EP1078929A2 - Sterically hindered amines - Google Patents

Abstract

2,2,6,6-tetramethylpiperidine-4,5'-spiro-4'-oxazolidinone derivatives (I) are new. 2,2,6,6-tetramethylpiperidine-4,5'-spiro-4'-oxazolidinone derivatives of formula (I) are new: X1 = H, 1-22C alkyl, an oxygen radical, OH, NO, CH2CN, benzyl, allyl, 1-30C alkoxy, 5-12C cycloalkoxy, 6-10C aryloxy (optionally substituted by 1-5C alkyl, halogen or NO2), 7-20C aralkoxy (optionally ring-substituted by 1-5C alkyl, halogen or NO2), 3-10C alkenyl, 3-6C alkynyl, 1-10C acyl, halogen or phenyl (optionally substituted by 1-4C alkyl); X2 = H, CH2CH2COOX5, CH2CH(Me)COOX5 or 1-22C alkyl; X3, X4 = H, phenyl (optionally substituted by 1-4C alkyl) or 1-22C alkyl, at least one being branched 4-22C alkyl; X5 = 1-22C alkyl. Independent claims are also included for the following: (1) a mixture of a compound (I) and one or more sterically hindered amines selected from 10 formulae given in the specification; (2) a mixture of a compound (I) and one or more polymeric HALS compounds selected from 7 formulae given in the specification; (3) a mixture of compounds (I) and one or more organophosphite or organophosphonite compounds selected from 7 formulae given in the specification; (4) a mixture of compounds (I) and ultraviolet absorbers selected from 2-hydroxybenzophenones, 2-hydroxyphenyl-benzotriazoles, cinnamic acid derivatives and oxanilides; (5) a mixture of compounds (I) and zeolites or hydrotalcites; (6) a mixture of compounds (I) or the mixtures of (1)-(3) and one or more N,N-dialkyl hydroxylamines; (7) a mixture of compounds (I) and one or more acid-binding costabilizers selected from metal carboxylates, metal oxides, metal hydroxides, metal carbonates, zeolites and hydrotalcites.

Description

The present invention relates to sterically hindered amines as stabilizers for organic material, especially for polymers, and on mixtures with others Stabilizers.

It is known that organic materials are damaged by light, radiation, heat or oxygen. There are already many publications that describe compounds for stabilizing organic material against these influences. These are mostly free radical scavengers and, in particular in connection with light stabilizers, compounds that are able to decompose hydroperoxides, quenchers (quenchers for excited states) or UV absorbers. Heat stabilizers are often sterically hindered phenols. The stabilizers, which provide protection against thermal degradation during processing especially for organic polymers, it is often to phosphites or phosphonites (see. R. Gächter, H. Müller, Plastics Additives Handbook, ^3rd Ed., Hanser Verlag, Munich 1990).

The stabilizer classes mentioned often have specific disadvantages, which besides the desired effect occur. Especially regarding color behavior, interaction with Pigments, compatibility of various stabilizers used at the same time with each other and with the material to be stabilized, resistance to chemicals and Water (sensitivity to hydrolysis), storage stability, migration behavior, improvement of Stabilization against the damaging effects of heat and oxygen in the course of Polymer processing and improving stabilization against the damaging Influences of light, radiation, heat in long-term use are in great demand new stabilizers.

In the field of light stabilizers, steric in particular have been around for many years hindered amines, which intervene in the mechanism of polymer degradation. In the More recently, it has also been recognized that this class of compound also make a certain contribution to long-term stabilization against thermally induced degradation of contribute organic polymers (see e.g. P. Gijsman in Polymer Degradation and Stability 43, (1994) 171-174 and F. Gugumus in Polymer Degradation and Stability 44, (1994) 299-322). In contrast to the long-term stabilization of polymers, a stabilizing effect of the compound class of sterically hindered amines in Connection with the thermal degradation of organic polymers in the course of their Processing never observed before.

In connection with the thermally induced degradation of organic polymers in the In the recent past, the course of their processing was recognized as stabilizing Effect of established stabilizers (antioxidants based on sterically hindered Phenols and phosphites / phosphonites) by adding special Processing stabilizers can be significantly improved. Here is especially on the Use of lactones indicated (see, inter alia, EP-A-842 975, EP-A-839 623). A Efficacy of sterically hindered amines has never been described in this context.

DE-A-2606026 describes sterically hindered amines, which are a spirostructure exhibit. The connections described there are used exclusively as Light protection agents presented.

It has now surprisingly been found that a subgroup of the formula (1) which is not detailed in DE-A-2 606 026 and in which at least one of the two radicals X ₃ or X ₄ (or else both) denotes a branched alkyl radical is exceptional high light protection. The light protection effect of compound (1) is significantly greater than the effect of the compounds described in DE-A-2606026 (cf. experimental part). In addition, the compounds of the formula (1) are notable for a process-stabilizing effect which they develop in particular in combination with sterically hindered phenols and phosphites / phosphonites in organic polymers. This property observed in representatives of compound class (1) is new and unexpected for sterically hindered amines.

worin

X₁

Wasserstoff, eine C₁-C₂₂-, vorzugsweise eine C₁-C₅-Alkylgruppe, insbesonders eine Methylgruppe; ein Sauerstoffradikal O*; -OH; -NO; -CH₂CN; Benzyl; Allyl; eine C₁-C₃₀-, vorzugsweise eine C₁-C₁₀-Alkoxygruppe; eine C₅-C₁₂-, vorzugsweise eine C₅-C₆-Cycloalkyloxygruppe; eine C₆-C₁₀-, vorzugsweise eine C₆-C₇-, insbesonders eine C₆-Aryloxygruppe, wobei der Arylrest zusätzlich noch durch eine C₁-C₅-Alkylgruppe oder ein Halogen oder eine Nitrogruppe substituiert sein kann; eine C₇-C₂₀-, vorzugsweise eine C₇-C₁₀-Arylalkyloxygruppe, wobei der Arylrest zusätzlich noch durch eine C₁-C₅-Alkylgruppe oder ein Halogen oder eine Nitrogruppe substituiert sein kann; eine C₃-C₁₀-, vorzugsweise eine C₃-C₆-Alkenylgruppe; eine C₃-C₆-Alkinylgruppe; eine C₁-C₁₀-, vorzugsweise eine C₁-C₅-Acylgruppe; Halogen; einen unsubstituierten oder durch C₁-C₄-, vorzugsweise durch C₁-C₂-Alkyl substituierten Phenylrest, bedeutet;

X₂

Wasserstoff, einen [CH₂-CH₂-C(O)-O-X₅]-Rest, einen [CH₂-C(CH₃)H-C(O)-O-X₅]-Rest; eine C₁-C₂₂-Alkylgruppe, vorzugsweise eine C₁-C₁₀-, insbesondere C₁-C₄-Alkylgruppe bedeutet;

X₃ und X₄

unabhängig voneinander Wasserstoff, einen unsubstituierten oder durch C₁-C₄-, vorzugsweise durch C₁-C₂-Alkyl substituierten Phenylrest oder eine C₁- C₂₂-, vorzugsweise eine verzweigte C₄-C₂₂-Alkylgruppe, wobei mindestens einer der zwei Reste X₃ oder X₄ eine verzweigte C₄-C₂₂-Alkylgruppe, vorzugsweise eine verzweigte C₄-C₁₀-, insbesondere eine verzweigte C₄-C₆-Alkylgruppe bedeuten; und worin

X₅

eine C₁-C₂₂-, vorzugsweise eine C₁₀-C₁₆-, insbesonders eine C₁₂-C₁₄-Alkylgruppe bedeutet.

The invention thus relates to stabilizers of the general formula (1)

wherein

X ₁

Hydrogen, a C ₁ -C ₂₂ , preferably a C ₁ -C ₅ alkyl group, in particular a methyl group; an oxygen radical O *; -OH; -NO; -CH ₂ CN; Benzyl; Allyl; a C ₁ -C ₃₀ , preferably a C ₁ -C ₁₀ alkoxy group; a C ₅ -C ₁₂ , preferably a C ₅ -C ₆ cycloalkyloxy group; a C ₆ -C ₁₀ , preferably a C ₆ -C ₇ , in particular a C ₆ aryloxy group, it being possible for the aryl radical to be additionally substituted by a C ₁ -C ₅ alkyl group or a halogen or a nitro group; a C ₇ -C ₂₀ , preferably a C ₇ -C ₁₀ arylalkyloxy group, where the aryl radical can additionally be substituted by a C ₁ -C ₅ alkyl group or a halogen or a nitro group; a C ₃ -C ₁₀ , preferably a C ₃ -C ₆ alkenyl group; a C ₃ -C ₆ alkynyl group; a C ₁ -C ₁₀ , preferably a C ₁ -C ₅ acyl group; Halogen; is an unsubstituted or substituted by C ₁ -C ₄ , preferably substituted by C ₁ -C ₂ alkyl;

X ₂

Hydrogen, a [CH ₂ -CH ₂ -C (O) -OX ₅ ] residue, a [CH ₂ -C (CH ₃ ) HC (O) -OX ₅ ] residue; is a C ₁ -C ₂₂ alkyl group, preferably a C ₁ -C ₁₀ , in particular C ₁ -C ₄ alkyl group;

X ₃ and X ₄

independently of one another hydrogen, an unsubstituted or C ₁ -C ₄ -, preferably substituted by C ₁ -C ₂ -alkyl-substituted phenyl radical or a C ₁ - C ₂₂ -, preferably a branched C ₄ -C ₂₂ -alkyl group, at least one of the two radicals X ₃ or X _{4 represent} a branched C ₄ -C ₂₂ alkyl group, preferably a branched C ₄ -C ₁₀ -, in particular a branched C ₄ -C ₆ alkyl group; and in what

X ₅

is a C ₁ -C ₂₂ , preferably a C ₁₀ -C ₁₆ , in particular a C ₁₂ -C ₁₄ alkyl group.

According to the invention, the compounds of the formula (1) can also be advantageously used in Mixture with other stabilizers are used, especially in a mixture with Organophosphites and / or organophosphonites plus optionally sterically hindered Phenols and / or other sterically hindered amines (HALS). The mixtures can also contain acid scavengers (basic costabilizers); in mixtures, which contain sterically hindered phenols can also with advantage sulfur-containing costabilizers are present.

The compounds of formula (1) are conveniently in one Concentration range of 0.001-5, preferably 0.002-0.05 wt .-%, based on the stabilizing organic material used; each of the remaining components can be in a concentration range of 0.001-5, preferably 0.01-1.0 wt .-%, are present.

Hindered amines come for the purposes of the present invention monomeric as well as polymeric HALS stabilizers into consideration, also mixtures of polymers with monomeric HALS stabilizers, such as. In EP-A-80 431 and EP-A-632 092.

worin

R¹

Wasserstoff, C₅-C₇-Cycloalkyl oder eine C₁-C₁₂-Alkylgruppe und

R⁴

entweder Wasserstoff oder eine C₁-C₂₂-Alkylgruppe, ein Sauerstoffradikal O*, -OH, -NO-, CH₂CN, Benzyl, Allyl, eine C₁-C₃₀-Alkoxygruppe, eine C₅-C₁₂-Cycloalkyloxygruppe, eine C₆-C₁₀-Aryloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann, eine C₇-C₂₀-Aralkyloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann, eine C₃-C₁₀-Alkenylgruppe, eine C₃-C₆-Alkinylgruppe, eine C₁-C₁₀-Acylgruppe, Halogen, unsubstituiertes oder am Phenylring durch C₁-C₄-Alkyl substituiertes C₇-C₉-Phenylalkyl,

R⁶

einen ein oder mehrfach durch Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Cyan, Carboxy, Nitro, Amino, C₁-C₄ -Alkylamino, C₁-C₄-Dialkylamino, oder Acyl substituierten aromatischen Rest,

o

1 oder 2; bedeutet.

worin

R¹ und R⁴

die weiter oben angeführten Bedeutungen haben,

p

1 oder 2; und

für p = 1

R⁷ C₁-C₂₂-Alkyl, C₂-C₁₈-Oxaalkyl, C₂-C₁₈-Thiaalkyl, C₂-C₁₈-Azaalkyl oder C₂-C₈-Alkenyl,

für p = 2

R⁷ C₁-C₂₂-Alkylen, C₂-C₁₈-Oxaalkylen, C₂-C₁₈-Thiaalkylen, C₂-C₁₈-Azaalkylen oder C₂-C₈-Alkenylen, bedeutet.

worin

R¹ und R⁴

die weiter oben angeführten Bedeutungen haben,

R⁸ und R⁹

unabhängig voneinander Wasserstoff, C₁-C₆-Alkyl, C₇-C₁₂-Aralkyl, -Aryl oder -Carbonsäureester,

R⁸ und R⁹

zusammen eine Tetra- oder Pentamethylgruppe bedeuten.

worin

R¹ und R⁴

die weiter oben angeführten Bedeutungen haben,

R² und R³

unabhängig voneinander ein Wasserstoffatom, eine C₁-C₁₈ -Alkylgruppe oder zusammen mit dem sie verbindenden C-Atom einen Ring der Ringgrösse 5 bis 13 oder zusammen mit dem sie bindenden C-Atom eine Gruppe der Formel (IV),

R⁴ und R⁵

unabhängig voneinander entweder Wasserstoff oder eine C₁-C₂₂ -Alkylgruppe, ein Sauerstoffradikal O*, -OH, -NO, -CH₂CN, Benzyl, Allyl, eine C₁-C₃₀-Alkyloxygruppe, eine C₅-C₁₂-Cycloalkyloxygruppe, eine C₆-C₁₀-Aryloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann, eine C₇-C₂₀-Arylalkyloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann, eine C₃-C₁₀- Alkenylgruppe, eine C₃-C₆-Alkinylgruppe, eine C₁-C₁₀-Acylgruppe, Halogen, unsubstituiertes oder am Phenylring durch C₁-C₄-Alkyl substituiertes C₇-C₉-Phenylalkyl bedeuten.

q

eine Zahl von 1 oder 2,

R¹⁰

Wasserstoff, Methyl, Phenyl oder Carb-C₁-C₂₁-Alkoxy,

R¹¹

Wasserstoff oder Methyl,

R¹²

für q = 1 Wasserstoff, C₁-C₂₁-Alkyl, C₂-C₂₂-Alkenyl, C₅-C₁₂-Cycloalkyl, ein Radikal der Formel

bedeutet, wobei R¹ und R⁵ die weiter oben angeführte Bedeutung haben, und

R¹²

für q = 2 C₁-C₁₈-Alkylen, C₅-C₉-Cycloalkylen oder Arylen bedeutet.

wobei R¹, R⁴, R⁷ und p die oben genannten Definitionen besitzen.

wobei R¹, R⁴, R⁷ und p die oben genannten Definitionen besitzen.

wobei

R¹, R⁴

die oben genannten Definitionen besitzen,

R³⁰

Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₂-Cycloalkyl, Phenyl oder C₇-C₉-Phenylalkyl, und

a

eine Zahl von 1 bis 10 bedeutet.

wobei

R¹ und R⁴

die obige Bedeutung hat und

R⁷

die in der Formel A2 für p=1 definierte Bedeutung hat.

The compounds of the formula (1) can be mixed particularly advantageously with monomeric HALS stabilizers of the formulas A1 to A10.

wherein

R ¹

Hydrogen, C ₅ -C ₇ cycloalkyl or a C ₁ -C ₁₂ alkyl group and

R ⁴

either hydrogen or a C ₁ -C ₂₂ alkyl group, an oxygen radical O *, -OH, -NO-, CH ₂ CN, benzyl, allyl, a C ₁ -C ₃₀ alkoxy group, a C ₅ -C ₁₂ cycloalkyloxy group, a C ₆ -C ₁₀ aryloxy group, where the aryl radical may additionally be substituted, a C ₇ -C ₂₀ aralkyloxy group, where the aryl radical may additionally be substituted, a C ₃ -C ₁₀ alkenyl group, a C ₃ -C _6- alkynyl group, a C ₁ -C ₁₀ -acyl group, halogen, C ₇ -C ₉ -phenylalkyl which is unsubstituted or substituted on the phenyl ring by C ₁ -C ₄ -alkyl,

R ⁶

one or more times by hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, carboxy, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, or Acyl substituted aromatic radical,

O

1 or 2; means.

wherein

R ¹ and R ⁴

have the meanings given above,

p

1 or 2; and

for p = 1

R ^{7 is} C ₁ -C ₂₂ alkyl, C ₂ -C ₁₈ oxaalkyl, C ₂ -C ₁₈ thiaalkyl, C ₂ -C ₁₈ azaalkyl or C ₂ -C ₈ alkenyl,

for p = 2

R ^{7 is} C ₁ -C ₂₂ alkylene, C ₂ -C ₁₈ oxaalkylene, C ₂ -C ₁₈ thiaalkylene, C ₂ -C ₁₈ azaalkylene or C ₂ -C ₈ alkenylene.

wherein

R ¹ and R ⁴

have the meanings given above,

R ⁸ and R ⁹

independently of one another hydrogen, C ₁ -C ₆ alkyl, C ₇ -C ₁₂ aralkyl, aryl or carboxylic acid esters,

R ⁸ and R ⁹

together represent a tetra or pentamethyl group.

wherein

R ¹ and R ⁴

have the meanings given above,

R ² and R ³

independently of one another a hydrogen atom, a C ₁ -C ₁₈ alkyl group or together with the carbon atom connecting them a ring of ring size 5 to 13 or together with the carbon atom binding them a group of the formula (IV),

R ⁴ and R ⁵

independently of one another either hydrogen or a C ₁ -C ₂₂ alkyl group, an oxygen radical O *, -OH, -NO, -CH ₂ CN, benzyl, allyl, a C ₁ -C ₃₀ alkyloxy group, a C ₅ -C ₁₂ - Cycloalkyloxy group, a C ₆ -C ₁₀ aryloxy group, where the aryl radical may additionally be substituted, a C ₇ -C ₂₀ arylalkyloxy group, where the aryl radical may additionally be substituted, a C ₃ -C ₁₀ alkenyl group, a C ₃ -C ₆ alkynyl group, a C ₁ -C ₁₀ acyl group, halogen, C ₇ -C ₉ phenylalkyl which is unsubstituted or substituted on the phenyl ring by C ₁ -C ₄ alkyl.

q

a number of 1 or 2,

R ¹⁰

Hydrogen, methyl, phenyl or carb-C ₁ -C ₂₁ alkoxy,

R ¹¹

Hydrogen or methyl,

R ¹²

for q = 1 hydrogen, C ₁ -C ₂₁ alkyl, C ₂ -C ₂₂ alkenyl, C ₅ -C ₁₂ cycloalkyl, a radical of the formula

means, wherein R ¹ and R ^{5 have} the meaning given above, and

R ¹²

for q = 2 is C ₁ -C ₁₈ alkylene, C ₅ -C ₉ cycloalkylene or arylene.

where R ¹ , R ⁴ , R ⁷ and p have the above definitions.

where R ¹ , R ⁴ , R ⁷ and p have the above definitions.

in which

R ¹ , R ⁴

have the above definitions,

R ³⁰

Hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl or C ₇ -C ₉ phenylalkyl, and

a

means a number from 1 to 10.

in which

R ¹ and R ⁴

has the above meaning and

R ⁷

has the meaning defined in formula A2 for p = 1.

wobei

R¹, R⁴ und R³⁰

die oben angegebene Bedeutung haben,

n_5', n_5" und n_5"'

unabhängig voneinander eine Zahl von 2 bis 12 ist.

A product A10 obtainable by reacting a polyamine of the formula A10a with formula A10b:

in which

R ¹ , R ⁴ and R ³⁰

have the meaning given above,

n _{5 '} , n _{5 "} and n _5"'

is independently a number from 2 to 12.

R¹

Wasserstoff oder eine C₁-C₄-Alkylgruppe,

R² und R³

unabhängig voneinander ein Wasserstoffatom, eine C₁-C₈-Alkylgruppe oder zusammen mit dem sie verbindenden C-Atom einen Ring der Ringgrösse 6 bis 12, oder zusammen mit dem sie bindenden C-Atom eine Gruppe der Formel (IV),

R⁴ und R⁵

unabhängig voneinander entweder Wasserstoff oder eine C₁-C₅-Alkylgruppe, ein Sauerstoffradikal O*, -OH, -NO, -CH₂CN, Benzyl, Allyl, eine C₁-C₁₀-Alkyloxygruppe, eine C₅-C₆-Cycloalkyloxygruppe, eine C₆-C₇-Aryloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann; eine C₇-C₁₀-Arylalkyloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann, eine C₃-C₆-Alkenylgruppe, eine C₃-C₆-Alkinylgruppe, eine C₁-C₄-Acylgruppe, Halogen, unsubstituiertes oder am Phenylring durch C₁-C₂-Alkyl substituiertes C₇-C₉-Phenylalkyl,

R⁷

ein geradkettiges C₁-C₁₀-Alkylen (für p = 2); C₁-C₁₂-Alkyl (für p = 1),

R⁸ und R⁹

unabhängig voneinander Wasserstoff, C₁-C₂-Alkyl, C₇-C₈-Arylalkyl, Aryl- oder Carbonsäureester,

R¹⁰

Wasserstoff, Methyl, Phenyl oder C₁-C₂-Alkoxy,

R¹¹

Wasserstoff oder Methyl,

R¹²

für q = 1 Wasserstoff, C₁-C₁₆-Alkyl, C₂-C₁₆-Alkenyl, C₅-C₆-Cycloalkyl, ein Radikal der Formel

R¹²

für q = 2 C₁-C₁₆-Alkylen, C₅-C₆-Cycloalkylen oder Arylen bedeutet,

R³⁰

Wasserstoff, C₁-C₈-Alkyl, C₅-C₇-Cycloalkyl, Phenyl oder C₇-C₈-Phenylalkyl,

a

1 bis 5,

o

1 und

p

2 bis 5 bedeutet.

Mixtures with compounds of the formulas A1 to A10 in which

R ¹

Hydrogen or a C ₁ -C ₄ alkyl group,

R ² and R ³

independently of one another a hydrogen atom, a C ₁ -C ₈ -alkyl group or together with the carbon atom connecting them a ring of ring size 6 to 12, or together with the carbon atom binding them a group of the formula (IV),

R ⁴ and R ⁵

independently of one another either hydrogen or a C ₁ -C ₅ alkyl group, an oxygen radical O *, -OH, -NO, -CH ₂ CN, benzyl, allyl, a C ₁ -C ₁₀ alkyloxy group, a C ₅ -C ₆ - Cycloalkyloxy group, a C ₆ -C ₇ aryloxy group, it being possible for the aryl radical to be additionally substituted; a C ₇ -C ₁₀ arylalkyloxy group, where the aryl radical may additionally be substituted, a C ₃ -C ₆ alkenyl group, a C ₃ -C ₆ alkynyl group, a C ₁ -C ₄ acyl group, halogen, unsubstituted or am Phenyl ring substituted by C ₁ -C ₂ alkyl-substituted C ₇ -C ₉ phenylalkyl,

R ⁷

a straight chain C ₁ -C ₁₀ alkylene (for p = 2); C ₁ -C ₁₂ alkyl (for p = 1),

R ⁸ and R ⁹

independently of one another hydrogen, C ₁ -C ₂ alkyl, C ₇ -C ₈ arylalkyl, aryl or carboxylic acid esters,

R ¹⁰

Hydrogen, methyl, phenyl or C ₁ -C ₂ alkoxy,

R ¹¹

Hydrogen or methyl,

R ¹²

for q = 1 hydrogen, C ₁ -C ₁₆ alkyl, C ₂ -C ₁₆ alkenyl, C ₅ -C ₆ cycloalkyl, a radical of the formula

R ¹²

for q = 2 is C ₁ -C ₁₆ alkylene, C ₅ -C ₆ cycloalkylene or arylene,

R ³⁰

Hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₇ cycloalkyl, phenyl or C ₇ -C ₈ phenylalkyl,

a

1 to 5,

O

1 and

p

2 to 5 means.

R¹

Methyl,

R² und R³

zusammen mit dem sie verbindenden C-Atom einen Ring der Ringgrösse 12, oder zusammen mit dem sie bindenden C-Atom eine Gruppe der Formel (IV),

R⁴ und R⁵

unabhängig voneinander Wasserstoff, Methyl, Acetyl, Octyloxy oder Cyclohexyloxy,

R⁶

p-Methoxyphenyl,

R⁷

Octamethylen, Hexamethylen oder Ethylen (für p = 2), Dodecyl (für p =1),

R⁸ und R⁹

Wasserstoff,

R¹⁰

Wasserstoff,

R¹¹

Wasserstoff,

R¹²

Dodecamethylen oder Tetradecamethylen,

R³⁰

Cyclohexyl oder n-Butyl,

a

gleich 2,

o

gleich 1,

p

gleich 2 und

q

gleich 1 ist.

Mixtures with compounds of the formulas A1 to A10, in which

R ¹

Methyl,

R ² and R ³

together with the carbon atom connecting them a ring of ring size 12, or together with the carbon atom binding them a group of the formula (IV),

R ⁴ and R ⁵

independently of one another hydrogen, methyl, acetyl, octyloxy or cyclohexyloxy,

R ⁶

p-methoxyphenyl,

R ⁷

Octamethylene, hexamethylene or ethylene (for p = 2), dodecyl (for p = 1),

R ⁸ and R ⁹

Hydrogen,

R ¹⁰

Hydrogen,

R ¹¹

Hydrogen,

R ¹²

Dodecamethylene or tetradecamethylene,

R ³⁰

Cyclohexyl or n-butyl,

a

equal to 2,

O

equal to 1,

p

equal to 2 and

q

is 1.

wobei

und R'=H, CH₃ The following compounds are particularly suitable in a mixture with compounds of the formula (1)

in which

and R '= H, CH ₃

In a particularly suitable embodiment of the invention, the mixture is used with compounds of formula (1) stabilizers based on sterically hindered amines such as ®Tinuvin 770, ®Tinuvin 765, ®Tinuvin 123, ®Hostavin N 20, ®Hostavin N 24, ®Uvinul 4049, ®Sanduvor PR 31, ®Uvinul 4050, ®Good-rite UV 3034 or ®Good-rite 3150, ®Sanduvor 3055, ®Sanduvor 3056, ®Sanduvor 3058, ®Chimassorb 119 and ®Chimassorb 905.

worin

R¹

Wasserstoff, C₅-C₇-Cycloalkyl oder eine C₁-C₁₂-Alkylgruppe,

R¹³

Wasserstoff oder Methyl,

R¹⁴

eine direkte Bindung oder C₁-C₁₀-Alkylen und

r

eine Zahl von 2 bis 50 bedeutet.

wobei

R¹ und R⁴

die weiter oben angegebenen Bedeutungen haben,

R¹⁵ und R¹⁸

unabhängig voneinander eine direkte Bindung oder eine Gruppe -N(R²²)-CO- R²³-CO-N(R²⁴)-,

R²² und R²⁴

unabhängig voneinander Wasserstoff, C₁-C₈-Alkyl, C₅-C₁₂-Cycloalkyl, Phenyl, C₇-C₉-Phenylalkyl, oder eine Gruppe der Formel

R²³

eine direkte Bindung oder C₁-C₄-Alkylen,

R¹⁶, R¹⁷, R²⁰, R²¹

unabhängig voneinander Wasserstoff, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl, Phenyl, oder eine Gruppe der Formel B2a,

R¹⁹

Wasserstoff, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl, C₇-C₉-Phenylalkyl, Phenyl oder eine Gruppe der Formel B2a bedeuten und

s

eine Zahl von 1 bis 50 ist.

wobei

R¹, R⁴ und s

die oben angegebenen Bedeutungen haben,

R²⁵, R²⁶, R²⁷, R²⁸ und R²⁹

unabhängig voneinander eine direkte Bindung oder C₁-C₁₀-Alkylen sind.

Particularly advantageous polymeric HALS stabilizers for mixing with compounds of the formula (1) are compounds of the formulas B1 to B7:

wherein

R ¹

Hydrogen, C ₅ -C ₇ cycloalkyl or a C ₁ -C ₁₂ alkyl group,

R ¹³

Hydrogen or methyl,

R ¹⁴

a direct bond or C ₁ -C ₁₀ alkylene and

r

means a number from 2 to 50.

in which

R ¹ and R ⁴

have the meanings given above,

R ¹⁵ and R ¹⁸

independently of one another a direct bond or a group -N (R ²² ) -CO- R ²³ -CO-N (R ²⁴ ) -,

R ²² and R ²⁴

independently of one another hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₉ phenylalkyl, or a group of the formula

R ²³

a direct bond or C ₁ -C ₄ alkylene,

R ¹⁶ , R ¹⁷ , R ²⁰ , R ²¹

independently of one another hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, or a group of the formula B2a,

R ¹⁹

Is hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₇ -C ₉ phenylalkyl, phenyl or a group of the formula B2a and

s

is a number from 1 to 50.

in which

R ¹ , R ⁴ and s

have the meanings given above,

R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹

are independently a direct bond or C ₁ -C ₁₀ alkylene.

wobei

R¹ und R⁴

die weiter oben angegebenen Bedeutungen haben,

n_5', n_5" und n_5"'

unabhängig voneinander eine Zahl von 2 bis 12 sind,

R³⁰

die oben angegebene Bedeutung hat; wobei B4 eine Verbindung der Formel B4-1, B4-2, B4-3

oder ein Gemisch daraus darstellt, worin

n₅

1 bis 20,

R⁴ und R³⁰

die oben angegebene Bedeutung haben.

wobei

r

die bei Formel B1 angegebene Bedeutung hat,

R³¹, R³³ und R³⁴

unabhängig voneinander Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₂-Cycloalkyl, durch C₁-C₄-Alkyl substituiertes C₅-C₁₂-Cycloalkyl, Phenyl, durch -OH und/oder C₁-C₁₀-Alkyl substituiertes Phenyl, C₇-C₉-Phenylalkyl, am Phenylrest durch -OH und/oder C₁-C₁₀-Alkyl substituiertes C₇-C₉-Phenylkalkyl oder eine Gruppe der Formel B5a bedeuten,

wobei R¹ und R⁵ die oben angegebenen Bedeutungen haben, und

R³²

C₂-C₁₈-Alkylen, C₅-C₇-Cycloalkylen oder C₁-C₄-Alkylendi(C₅-C₇-Cyloalkylen) ist, oder

die Reste R³¹, R³² und R³³

zusammen mit den Stickstoffatomen, an die sie gebunden sind, einen 5- bis 10-gliedrigen heterocyclischen Ring bilden, und wobei mindestens einer der Reste R³¹, R³³ und R³⁴ eine Gruppe der Formel B5a darstellt.

worin

R³¹, R³², R³³ und r

die oben angegebenen Bedeutungen haben,

R³⁵ und R³⁶

unabhängig voneinander die Definition von R³⁴ haben kann, oder

R³⁵ und R³⁶

zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5- bis 10-gliedrigen heterozyklischen Ring bilden, wobei dieser zusätzlich zum Stickstoff-Heteroatom noch ein oder mehrere Heteroatome, vorzugsweise ein Sauerstoffatom, enthalten kann und mindestens einer der Reste R³¹, R³³, R³⁵ und/oder R³⁶ eine Gruppe der Formel (B5a) darstellt.

wobei

R¹ und R⁴

die weiter oben angegebene Bedeutung haben,

s

die in Formel B3 angegebenen Bedeutung hat,

R³⁷

C₁-C₁₀-Alkyl, C₅-C₁₂-Cycloalkyl, durch C₁-C₄-Alkyl substituiertes C₅-C₁₂-Cycloalkyl, Phenyl oder durch C₁-C₁₀-Alkyl substituiertes Phenyl ist, und

R³⁸

C₃-C₁₀-Alkylen darstellt.

A product B4 obtainable by reacting a product obtained by reacting a polyamine of the formula B4a with cyanuric acid chloride with a compound of the formula B4b,

in which

R ¹ and R ⁴

have the meanings given above,

n _{5 '} , n _{5 "} and n _5"'

are independently a number from 2 to 12,

R ³⁰

has the meaning given above; where B4 is a compound of the formula B4-1, B4-2, B4-3

or a mixture thereof, wherein

n ₅

1 to 20,

R ⁴ and R ³⁰

have the meaning given above.

in which

r

has the meaning given for formula B1,

R ³¹ , R ³³ and R ³⁴

are independently hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ cycloalkyl, phenyl, substituted by -OH and / or C ₁ -C ₁₀ alkyl-substituted phenyl, C ₇ -C ₉ phenylalkyl substituted on the phenyl radical by -OH and / or C ₁ -C ₁₀ alkyl C ₇ -C ₉ -Phenylkalkyl or a group of the formula B5a,

wherein R ¹ and R ^{5 have} the meanings given above, and

R ³²

C ₂ -C ₁₈ alkylene, C ₅ -C ₇ cycloalkylene or C ₁ -C ₄ alkylene di (C ₅ -C ₇ cycloalkylene), or

the radicals R ³¹ , R ³² and R ³³

together with the nitrogen atoms to which they are attached form a 5- to 10-membered heterocyclic ring, and at least one of the radicals R ³¹ , R ³³ and R ^{34 represents} a group of the formula B5a.

wherein

R ³¹ , R ³² , R ³³ and r

have the meanings given above,

R ³⁵ and R ³⁶

can independently have the definition of R ³⁴ , or

R ³⁵ and R ³⁶

together with the nitrogen atom to which they are attached form a 5- to 10-membered heterocyclic ring, which in addition to the nitrogen heteroatom may contain one or more heteroatoms, preferably an oxygen atom, and at least one of the radicals R ³¹ , R ³³ , R ³⁵ and / or R ^{36 represents} a group of the formula (B5a).

in which

R ¹ and R ⁴

have the meaning given above,

s

has the meaning given in formula B3,

R ³⁷

C ₁ -C ₁₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ cycloalkyl, phenyl or C ₁ -C ₁₀ alkyl-substituted phenyl, and

R ³⁸

C ₃ -C ₁₀ alkylene.

The compounds described as components B1 to B4 are essentially known (some are commercially available) and can be prepared by known methods, for example as in US 4,233,412, US 4,340,534, US 4,857,595, DD-A-262 439 (Derwent 89-122 983/17, Chemical Abstracts 111: 58 964u), DE-A-4 239 437 (Derwent 94-177 274/22), US 4,529,760, US 4,477,615 and Chemical Abstracts - CAS No. 136 504-96-6 become.

Component B4 can, for example, in analogy to known processes Reaction of a polyamine of formula B4a with cyanuric acid chloride in a molar Ratio of 1: 2 to 1: 4 in the presence of anhydrous lithium, sodium or Potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, Benzene, dioxane or tert-amyl alcohol at a temperature of -20 ° C to + 10 ° C, preferred -10 ° C to + 10 ° C, especially 0 ° C to + 10 ° C, for 2 to 8 hours and subsequent reaction of the product obtained with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula B4b. The molar ratio of 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of formula B4a used for example 4: 1 to 8: 1. The amount of 2,2,6,6-tetramethyl-4-piperidylamine can be up be added once or in several portions every few hours.

The ratio of polyamine of the formula B4a: cyanuric acid chloride: 2,2,6,6-tetramethyl-4-piperidylamine is preferred of the formula B4b 1: 3: 5 to 1: 3: 6.

In general, component B4 can be, for example, by a compound of the formula B4-1, B4-2 or B4-3 can be played. It can also be a mixture of these three Connections exist.

A preferred meaning of formula B4-1 is

A preferred meaning of formula B4-2 is

A preferred meaning of formula B4-3 is

R¹

Wasserstoff oder eine C₁-C₄-Alkylgruppe,

R² und R³

unabhängig voneinander ein Wasserstoffatom, eine C₁-C₈-Alkylgruppe oder zusammen mit dem sie verbindenden C-Atom einen Ring der Ringgrösse 6 bis 12, oder zusammen mit dem sie bindenden C-Atom eine Gruppe der Formel (IV),

R⁴ und R⁵

unabhängig voneinander entweder Wasserstoff oder eine C₁-C₅-Alkylgruppe, ein Sauerstoffradikal O*, -OH, -NO, -CH₂CN, Benzyl, Allyl, eine C₁-C₁₀-Alkyloxygruppe, eine C₅-C₆-Cycloalkyloxygruppe, eine C₆-C₇-Aryloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann, eine C₇-C₁₀-Arylalkyloxygruppe, wobei der Arylrest zusätzlich noch substituiert sein kann, eine C₃-C₆-Alkenylgruppe, eine C₃-C₆-Alkinylgruppe, eine C₁-C₄-Acylgruppe, Halogen, unsubstituiertes oder am Phenylring durch C₁-C₂-Alkyl substituiertes C₇-C₉-Phenylalkyl bedeuten,

R¹³

Wasserstoff oder Methyl,

R¹⁴

C₁-C₅-Alkylen,

R¹⁷, R²¹

Wasserstoff oder C₁-C₄-Alkyl,

R¹⁵, R¹⁸

eine direkte Bindung,

R¹⁶, R²⁰

C₁-C₂₅-Alkyl, Phenyl,

R¹⁹

Wasserstoff, C₁-C₁₂-Alkyl oder eine Gruppe der Formel B2a

R²⁵, R²⁶, R²⁷, R²⁸ und R²⁹

unabhängig voneinander eine direkte Bindung oder C₁-C₅-Alkylen,

R³⁰

Wasserstoff, C₁-C₄-Alkyl, C₅-C₆-Cycloalkyl, Phenyl,

R³¹, R³³ und R³⁴

unabhängig voneinander Wasserstoff, C₁-C₁₀-Alkyl, C₅-C₆-Cycloalkyl oder eine Gruppe der Formel B5a bedeutet,

R³²

C₂-C₁₀-Alkylen, C₅-C₆-Cycloalkylen,

R³⁵ und R³⁶

unabhängig voneinander die Definition von R³⁴, oder R³⁵ und R³⁶ zusammen mit dem N-Atom, an das sie gebunden sind einen 5 bis 7-gliedrigen heterocyclischen Ring bilden, wobei dieser noch ein oder mehrere Heteroatome, vorzugsweise ein O-Atom enthalten kann und mindestens einer der Reste R³¹,R³³,R³⁵ und/oder R³⁶ eine Gruppe der Formel B5a darstellt,

R³⁷

C₁-C₅-Alkyl, C₅-C₆-Cycloalkyl oder Phenyl,

R³⁸

C₃-C₅-Alkylen und

n_5',n_5",n_5"'

2 bis 4 bedeuten.

For mixing with compounds of the formula (1), preference is given to compounds of the formulas B1 to B7, in which

R ¹

Hydrogen or a C ₁ -C ₄ alkyl group,

R ² and R ³

independently of one another a hydrogen atom, a C ₁ -C ₈ -alkyl group or together with the carbon atom connecting them a ring of ring size 6 to 12, or together with the carbon atom binding them a group of the formula (IV),

R ⁴ and R ⁵

independently of one another either hydrogen or a C ₁ -C ₅ alkyl group, an oxygen radical O *, -OH, -NO, -CH ₂ CN, benzyl, allyl, a C ₁ -C ₁₀ alkyloxy group, a C ₅ -C ₆ - Cycloalkyloxy group, a C ₆ -C ₇ aryloxy group, where the aryl radical may additionally be substituted, a C ₇ -C ₁₀ arylalkyloxy group, where the aryl radical may additionally be substituted, a C ₃ -C ₆ alkenyl group, a C ₃ -C ₆ -alkynyl group, a C ₁ -C ₄ -acyl group, halogen, unsubstituted or C ₇ -C ₉ -phenylalkyl which is substituted on the phenyl ring by C ₁ -C ₂ alkyl,

R ¹³

Hydrogen or methyl,

R ¹⁴

C ₁ -C ₅ alkylene,

R ¹⁷ , R ²¹

Hydrogen or C ₁ -C ₄ alkyl,

R ¹⁵ , R ¹⁸

a direct bond,

R ¹⁶ , R ²⁰

C ₁ -C ₂₅ alkyl, phenyl,

R ¹⁹

Hydrogen, C ₁ -C ₁₂ alkyl or a group of the formula B2a

R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹

independently of one another a direct bond or C ₁ -C ₅ alkylene,

R ³⁰

Hydrogen, C ₁ -C ₄ alkyl, C ₅ -C ₆ cycloalkyl, phenyl,

R ³¹ , R ³³ and R ³⁴

independently of one another is hydrogen, C ₁ -C ₁₀ alkyl, C ₅ -C ₆ cycloalkyl or a group of the formula B5a,

R ³²

C ₂ -C ₁₀ alkylene, C ₅ -C ₆ cycloalkylene,

R ³⁵ and R ³⁶

independently of one another, the definition of R ³⁴ , or R ³⁵ and R ³⁶ together with the N atom to which they are attached form a 5 to 7-membered heterocyclic ring, this ring also containing one or more heteroatoms, preferably an O atom and at least one of the radicals R ³¹ , R ³³ , R ³⁵ and / or R ^{36 represents} a group of the formula B5a,

R ³⁷

C ₁ -C ₅ alkyl, C ₅ -C ₆ cycloalkyl or phenyl,

R ³⁸

C ₃ -C ₅ alkylene and

n _{5 '} , n _{5 "} , n _5"'

2 to 4 mean.

R¹

Methyl,

R² und R³

zusammen mit dem sie verbindenden C-Atom einen Ring der Ringgrösse 12, oder zusammen mit dem sie bindenden C-Atom eine Gruppe der Formel (IV),

R⁴ und R⁵

unabhängig voneinander Wasserstoff, Acetyl, Methyl, Octyloxy oder Cyclohexyloxy,

R¹³

Wasserstoff,

R¹⁴

Ethylen,

R¹⁷, R²¹

Wasserstoff oder Methyl,

R¹⁵, R¹⁸

eine direkte Bindung,

R¹⁶, R²⁰

C₁-C₂₅-Alkyl, Phenyl,

R¹⁹

Hexadecyl oder eine Gruppe der Formel B2a,

R²⁵, R²⁷

Methylen,

R²⁶

eine direkte Bindung,

R²⁸

2,2-Dimethylethylen,

R²⁹

1,1-Dimethylethylen,

R³⁰

n-Butyl,

R³¹, R³³ und R³⁴

unabhängig voneinander Isooctyl, Cyclohexyl oder 2,2,6,6-Tetramethylpiperid-4-yl bedeuten, wobei mindestens einer der Reste R³¹, R³³ und R³⁴ 2,2,6,6-Tetramethylpiperid-4-yl bedeuten muss,

R³²

Hexamethylen,

R³⁵ und R³⁶

unabhängig voneinander die Definition von R³⁴, oder R³⁵ und R³⁶ zusammen mit dem N-Atom, an das sie gebunden sind einen 6-gliedrigen heterocyclischen Ring bilden, wobei dieser noch ein Sauerstoffatom enthält und folglich Morpholin ist, wobei mindestens einer der Reste R³¹,R³³,R³⁵ und/oder R³⁶ einen Rest 2,2,6,6-Tetramethylpiperid-4-yl bedeuten muss,

R³⁷

Methyl,

R³⁸

Trimethylen,

n_5',n_5",n_5"'

2 bis 4 bedeuten.

Very particularly preferred for mixing with compounds of the formula (1) are compounds of the formulas B1 to B7 in which

R ¹

Methyl,

R ² and R ³

together with the carbon atom connecting them a ring of ring size 12, or together with the carbon atom binding them a group of the formula (IV),

R ⁴ and R ⁵

independently of one another hydrogen, acetyl, methyl, octyloxy or cyclohexyloxy,

R ¹³

Hydrogen,

R ¹⁴

Ethylene,

R ¹⁷ , R ²¹

Hydrogen or methyl,

R ¹⁵ , R ¹⁸

a direct bond,

R ¹⁶ , R ²⁰

C ₁ -C ₂₅ alkyl, phenyl,

R ¹⁹

Hexadecyl or a group of the formula B2a,

R ²⁵ , R ²⁷

Methylene,

R ²⁶

a direct bond,

R ²⁸

2,2-dimethylethylene,

R ²⁹

1,1-dimethylethylene,

R ³⁰

n-butyl,

R ³¹ , R ³³ and R ³⁴

independently of one another is isooctyl, cyclohexyl or 2,2,6,6-tetramethylpiperid-4-yl, where at least one of the radicals R ³¹ , R ³³ and R ^{34 must be} 2,2,6,6-tetramethylpiperid-4-yl,

R ³²

Hexamethylene,

R ³⁵ and R ³⁶

independently of one another the definition of R ³⁴ , or R ³⁵ and R ³⁶ together with the N atom to which they are attached form a 6-membered heterocyclic ring, this ring also containing an oxygen atom and consequently being morpholine, at least one of the radicals R ³¹ , R ³³ , R ³⁵ and / or R ^{36 must represent} a 2,2,6,6-tetramethylpiperid-4-yl radical,

R ³⁷

Methyl,

R ³⁸

Trimethylene,

n _{5 '} , n _{5 "} , n _5"'

2 to 4 mean.

ein Produkt B'10 erhältlich durch Umsetzung eines durch Reaktion eines Polyamins der Formel B'10a: H₂N-(CH₂)₃-NH-(CH₂)₂-NH-(CH₂)₃-NH₂ mit Cyanursäurechlorid erhaltenen Produktes mit einer Verbindung der Formel (B'10b)

wobei B'10 eine Verbindung der Formel B4-1', B4-2', B4-3'

oder ein Gemisch daraus bedeutet, wobei n₅ 1 bis 20 bedeutet.When mixed with compounds of the formula (1), the polymeric HALS compounds are very particularly preferably the following substances:

a product B'10 obtainable by reacting one by reacting a polyamine of the formula B'10a: H ₂ N- (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -NH ₂ product obtained with cyanuric acid chloride with a compound of the formula (B'10b)

where B'10 is a compound of the formula B4-1 ', B4-2', B4-3 '

or a mixture thereof, where n _{5 is} 1 to 20.

Particularly preferred for mixing with compounds of the formula (1) are ®Chimassorb 944, ®Tinuvin 622, ®Dastib 1082, ®Uvasorb HA 88, ®Uvinul 5050, ®Lowilite 62, ®Uvasil 299, ®Cyasorb 3346, ®MARK LA 63, ®MARK LA 68 or ®Luchem B 18.

Combinations are also suitable for mixing with compounds of the formula (1) polymeric HALS stabilizers, such as. B. described in EP-A-252 877, EP-A-709 426, Research Disclosure Jan. 1993, No. 34 549 and EP-A-723 990.

worin die Indices ganzzahlig sind und n' für 2, 3 oder 4; u für 1 oder 2; t für 2 oder 3; y für 1, 2 oder 3; und z für 1 bis 6 steht; A', wenn n' 2 ist, Alkylen mit 2 bis 18 Kohlenstoffatomen; durch -S-, -O- oder -NR'₄- unterbrochenes Alkylen mit 2 bis 12 Kohlenstoffatomen; ein Rest einer der Formeln

oder Phenylen ist;

A'

wenn n' 3 ist, ein Rest der Formel -C_rH_2r-1 ist;

A'

wenn n'4 ist, den Rest der Formel C(CH₂)₄- bedeutet;

A"

die Bedeutung von A', wenn n' 2 ist, hat;

B'

einen Rest der Formel -CH₂-; -CHR'₄-; -CR'₁R'₄-; -S- oder eine direkte Bindung darstellt; oder C₅-C₇-Cycloalkyliden; oder mit 1 bis 4 C₁-C₄-Alkylresten in Position 3, 4 und/oder 5 substituierters Cyclohexyliden bedeutet,

D'

wenn u 1 ist, Methyl und, wenn u 2 ist, -CH₂OCH₂- bedeutet;

E'

wenn y 1 ist, Alkyl mit 1 bis 18 Kohlenstoffatomen, Phenyl, ein Rest der Formel -OR'₁ oder Halogen ist;

E'

wenn y 2 ist, ein Rest der Formel -O-A"-O- ist;

E'

wenn y 3 ist, ein Rest der Formel R'₄C(CH₂O)₃- oder N(CH₂-CH₂-O-)₃ ist;

Q'

für den Rest eines mindestens z-wertigen Alkohols oder Phenols steht, wobei dieser über das (die) alkoholische(n) bzw. phenolische(n) O-Atom(e) an das (die) P-Atom(e) gebunden ist;

R'₁, R'₂ und R'₃

unabhängig voneinander Alkyl mit 1 bis 30 Kohlenstoffatomen; mit Halogen, -COOR₄', -CN oder -CONR₄'R₄' substituiertes Alkyl mit 1 bis 18 Kohlenstoffatomen; durch -S-, -O- oder -NR'₄- unterbrochenes Alkyl mit 2 bis 18 Kohlenstoffatomen; Phenyl-C₁-C₄-alkyl; Cycloalkyl mit 5 bis 12 Kohlenstoffatomen; Phenyl oder Naphthyl; mit Halogen, 1 bis 3 Alkylresten oder Alkoxyresten mit insgesamt 1 bis 18 Kohlenstoffatomen oder mit Phenyl-C₁-C₄-Alkyl substituiertes Phenyl oder Naphthyl; oder ein Rest der Formel

sind, worin w eine ganze Zahl aus dem Bereich 3 bis 6 bedeutet;

R'4

beziehungsweise die Reste R'₄ unabhängig voneinander Wasserstoff, Alkyl mit 1 bis 18 Kohlenstoffatomen, Cycloalkyl mit 5 bis 12 Kohlenstoffatomen, oder Phenylalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil;

R'₅ und R'₆

unabhängig voneinander Wasserstoff, Alkyl mit 1 bis 8, Kohlenstoffatomen oder Cycloalkyl mit 5 oder 6 Kohlenstoffatomen sind;

R'₇ und R'₈

im Fall t = 2 unabhängig voneinander C₁-C₄-Alkyl oder zusammen einen 2,3-Dehydropentamethylenrest darstellen; und

R'₇ und R'₈

im Fall t = 3, Methyl bedeuten;

die Substituenten R'14

unabhängig voneinander Wasserstoff, Alkyl mit 1 bis 9 Kohlenstoffatomen oder Cyclohexyl sind;

die Substituenten R'₁₅

unabhängig voneinander Wasserstoff oder Methyl; und

R'₁₆

Wasserstoff oder C₁-C₄-Alkyl darstellt und im Fall, dass mehrere Reste R'₁₆ vorhanden sind, die Reste R'₁₆ gleich oder verschieden sind;

X' und Y'

jeweils eine direkte Bindung oder -O- darstellen; und

z

eine direkte Bindung; -CH₂-; -C(R'₁₆)₂- oder -S- ist.

Suitable organophosphites or organophosphonites for mixing with compounds of the formula (1) are compounds of the formulas C1 to C7:

where the indices are integers and n 'for 2, 3 or 4; u for 1 or 2; t for 2 or 3; y for 1, 2 or 3; and z represents 1 to 6; A ', when n' is 2, alkylene of 2 to 18 carbon atoms; alkylene with 2 to 12 carbon atoms interrupted by -S-, -O- or -NR '₄; a remainder of one of the formulas

or is phenylene;

A '

when n '3 is a radical of the formula -C _r H _2r-1 ;

A '

when n'4 is the radical of the formula C (CH ₂ ) ₄ -;

A "

has the meaning of A 'when n' is 2;

B '

a radical of the formula -CH ₂ -; -CHR ' ₄ -; -CR ' ₁ R' ₄ -; -S- or a direct bond; or C ₅ -C ₇ cycloalkylidene; or with 1 to 4 C ₁ -C ₄ alkyl radicals in position 3, 4 and / or 5 substituted cyclohexylidene,

D '

when u is 1, methyl and when u is 2, -CH ₂ OCH ₂ -;

E '

when y is 1, alkyl having 1 to 18 carbon atoms, phenyl, a radical of the formula -OR ' ₁ or halogen;

E '

when y is 2 is a radical of formula -OA "-O-;

E '

when y is 3, a radical of the formula R ' _{4 is} C (CH ₂ O) ₃ - or N (CH ₂ -CH ₂ -O-) ₃ ;

Q '

represents the remainder of an at least z-valent alcohol or phenol, which is bound to the P atom (s) via the alcoholic or phenolic O atom (s);

R ' ₁ , R' ₂ and R ' ₃

independently of one another alkyl having 1 to 30 carbon atoms; alkyl with 1 to 18 carbon atoms substituted with halogen, -COOR ₄ ', -CN or -CONR ₄ ' R ₄ '; alkyl interrupted by -S-, -O- or -NR ' ₄ - having 2 to 18 carbon atoms; Phenyl-C ₁ -C ₄ alkyl; Cycloalkyl of 5 to 12 carbon atoms; Phenyl or naphthyl; phenyl or naphthyl substituted with halogen, 1 to 3 alkyl radicals or alkoxy radicals with a total of 1 to 18 carbon atoms or with phenyl-C ₁ -C ₄ -alkyl; or a residue of the formula

where w is an integer ranging from 3 to 6;

R'4

or the radicals R ' ₄ independently of one another are hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or phenylalkyl having 1 to 4 carbon atoms in the alkyl part;

R ' ₅ and R' ₆

are independently hydrogen, alkyl of 1 to 8, carbon atoms or cycloalkyl of 5 or 6 carbon atoms;

R ' ₇ and R' ₈

in the case t = 2 independently of one another represent C ₁ -C ₄ -alkyl or together a 2,3-dehydropentamethylene radical; and

R ' ₇ and R' ₈

in the case t = 3, mean methyl;

the substituents R'14

are independently hydrogen, alkyl of 1 to 9 carbon atoms or cyclohexyl;

the substituents R _'15

independently of one another hydrogen or methyl; and

R _'16

Represents hydrogen or C ₁ -C ₄ alkyl and, in the event that a plurality of radicals R _'16 are present, the radicals R' _{16 are} identical or different;

X 'and Y'

each represent a direct bond or -O-; and

e.g.

a direct bond; -CH ₂ -; -C (R _'16 ) ₂ - or -S-.

n'

für die Zahl 2 und y für die Zahl 1 oder 2 steht;

A'

Alkylen mit 2 bis 18 Kohlenstoffatomen; p-Phenylen oder p-Biphenylen ist;

E'

im Fall y = 1 C₁-C₁₈-Alkyl, -OR₁ oder Fluor; und im Fall y = 2 p-Biphenylen ist;

R'₁, R'₂ und R'₃

unabhängig voneinander Alkyl mit 1 bis 18 Kohlenstoffatomen; Phenyl-C₁-C₄-Alkyl; Cyclohexyl; Phenyl; mit 1 bis 3 Alkylresten mit insgesamt 1 bis 18 Kohlenstoffatomen substituiertes Phenyl bedeutet;

die Substituenten R'₁₄

unabhängig voneinander Wasserstoff oder Alkyl mit 1 bis 9 Kohlenstoffatomen sind;

R'₁₅

Wasserstoff oder Methyl ist;

X'

eine direkte Bindung;

Y'

-O-; und

Z'

eine direkte Bindung oder -CH(R'₁₆)- ist.

Particularly preferred for mixing with compounds of the formula (1) are phosphites or phosphonites of the formulas C1, C2, C5 or C6, in which

n '

represents the number 2 and y represents the number 1 or 2;

A '

Alkylene of 2 to 18 carbon atoms; is p-phenylene or p-biphenylene;

E '

in the case of y = 1 C ₁ -C ₁₈ alkyl, -OR ₁ or fluorine; and in the case of y = 2 p-biphenylene;

R ' ₁ , R' ₂ and R ' ₃

independently of one another alkyl having 1 to 18 carbon atoms; Phenyl-C ₁ -C ₄ alkyl; Cyclohexyl; Phenyl; phenyl substituted with 1 to 3 alkyl radicals with a total of 1 to 18 carbon atoms;

the substituents R _'14

are independently hydrogen or alkyl of 1 to 9 carbon atoms;

R _'15

Is hydrogen or methyl;

X '

a direct bond;

Y '

-O-; and

Z '

is a direct bond or -CH (R _'16 ) -.

n'

für die Zahl 2 und y für die Zahl 1 steht;

A'

p-Biphenylen ist;

E'

C₁-C₁₈-Alkoxy ist;

R'₁, R'₂ und R'₃

unabhängig voneinander mit 2 oder 3 Alkylresten mit insgesamt 2 bis 12 Kohlenstoffatomen substitutiertes Phenyl bedeutet;

die Substituenten R'₁₄

unabhängig voneinander Methyl oder tert.-Butyl sind;

R'₁₅

Wasserstoff ist;

X'

eine direkte Bindung;

Y'

-O-; und

Z'

eine direkte Bindung, -CH₂- oder -CH(CH₃)- ist.

Very particularly preferred for mixing with compounds of the formula (1) are phosphites or phosphonites of one of the formulas C1, C2, C5 or C6 in which

n '

represents the number 2 and y represents the number 1;

A '

is p-biphenylene;

E '

C ₁ -C ₁₈ alkoxy;

R ' ₁ , R' ₂ and R ' ₃

phenyl independently substituted with 2 or 3 alkyl radicals with a total of 2 to 12 carbon atoms;

the substituents R _'14

are independently methyl or tert-butyl;

R _'15

Is hydrogen;

X '

a direct bond;

Y '

-O-; and

Z '

is a direct bond, -CH ₂ - or -CH (CH ₃ ) -.

In der Formel C'3 befinden sich die beiden Phosphor-Substituenten hauptsächlich in 4- bzw. 4'-Stellung des Biphenylgrundgerüsts

In particular, the specific phosphorus compounds of the formulas C'1 to C'12 are to be mentioned for mixing with compounds of the formula (1):

In formula C'3, the two phosphorus substituents are mainly in the 4- or 4'-position of the biphenyl backbone

The phosphites and phosphonites mentioned are known compounds, some of them commercially available.

Verbindung (1) und ®Irgafos 38,

Verbindung (1) und ®Irgafos 12,

Verbindung (1) und ®Hostanox PAR 24,

Verbindung (1) und ®Hostanox OSP 1,

Verbindung (1) und ®Irgafos P-EPQ,

Verbindung (1) und ®Ultranox 626,

Verbindung (1) und ®Ultranox 618,

Verbindung (1) und ®Mark PEP-36 (von Asahi Denka),

Verbindung (1) und ®Mark HP10 (von Asahi Denka),

Verbindung (1) und ®Doverphos 9228

The following stabilizer mixtures are particularly suitable embodiments of the invention:

Compound (1) and ®Irgafos 38,

Compound (1) and ®Irgafos 12,

Compound (1) and ®Hostanox PAR 24,

Compound (1) and ®Hostanox OSP 1,

Compound (1) and ®Irgafos P-EPQ,

Compound (1) and ®Ultranox 626,

Compound (1) and ®Ultranox 618,

Compound (1) and ®Mark PEP-36 (from Asahi Denka),

Compound (1) and ®Mark HP10 (from Asahi Denka),

Compound (1) and ®Doverphos 9228

The combination of compounds (1) with phosphites and phosphonites is also suitable in excellent in the sense that the phosphite or phosphonite the effect of Compounds (1) in the stabilization of organic material in a synergistic Way supported. Synergistic effects of this kind are described in EP-A-359 276 and EP-A-567 117. Mixtures of compounds (1) with are particularly suitable Phosphites or phosphonites of the formulas C'1 to C'12.

The compounds (1) are also outstandingly suitable, with phosphite or Phosphonite, and / or a sterically hindered phenol and / or an acid scavenger to be combined. The combination of compounds (1) in is particularly suitable Mixtures with phosphite or phosphonite, phenol and acid scavenger, in a way as described in DE-A-19 537 140.

The compounds (1) and the mixtures described above are also suitable other stabilizers, especially with light stabilizers, such as. B. from the class of UV absorbers (2-hydroxybenzophenones or 2-hydroxyphenyl-benzotriazoles, Cinnamic acid derivatives, oxanilides and triazine derivatives) and / or nickel quenchers, in one synergistic way to be combined.

In the mixtures described above, the proportion of compounds of the formula (1) are between 1 and 99% by weight.

The compounds (1) are also suitable for use in combination with zeolites or Hydrotalcites, e.g. ®DHT4A analogous to EP-A-429 731.

The compounds (1) and the mixtures described above can also with one or more N, N-dialkyl-substituted hydroxylamines are combined, preferably with N, N-dioctadecylhydroxylamine.

Furthermore, the compounds (1) with one or more basic or other acid-binding costabilizers from the group of metal carboxylates, oxides, hydroxides, carbonates, and / or zeolites, and / or hydrotalcites, can be combined.

Preferred costabilizers are calcium stearate and / or magnesium stearate, and / or Magnesium oxide, and / or zinc oxide and / or carbonate-containing zinc oxide and / or hydrotalcite as well as metal salts of other organic acids such as Calcium lactate.

Particularly preferred costabilizers are ®Zinc oxide active, ®Zinc oxide transparent and / or one of the Hydrotalcite ®DHT 4A, ®DHT4 A2, ®Kyowaad 200, ®Kyowaad 300, ®Kyowaad 400, ®Kyowaad 500, ®Kyowaad 600, ®Kyowaad 700, ®Kyowaad 1000, ®Kyowaad 2000.

According to the invention, the compounds of formula (1), optionally in Combinations with other stabilizers, for stabilizing organic materials, especially polymeric organic materials, especially synthetic ones polymeric organic materials (plastics) used. Compounds of the formula (1), optionally in combinations with other stabilizers, according to the invention during their manufacture and processing or during their long-term use used, especially when the stabilized material under the influence of radiation, light or is particularly exposed to heat.

Examples of such plastics are:

a) radikalisch (gewöhnlich bei hohem Druck und hoher Temperatur)

b) mittels Katalysator, wobei der Katalysator gewöhnlich ein oder mehrere Metalle der Gruppe IVb, Vb, VIb oder VIII enthält. Diese Metalle besitzen gewöhnlich einen oder mehrere Liganden wie Oxide, Halogenide, Alkoholate, Ester, Ether, Amine, Alkyle, Alkenyle und/oder Aryle, die entweder π- oder σ-koordiniert sein können. Diese Metallkomplexe können frei oder auf Träger fixiert sein, wie beispielsweise auf aktiviertem Magnesiumchlorid, Titan(III)chlorid, Aluminiumoxid oder Siliziumoxid. Diese Katalysatoren können im Polymerisationsmedium löslich oder unlöslich sein. Die Katalysatoren können als solche in der Polymerisation aktiv sein, oder es können weitere Aktivatoren verwendet werden, wie beispielsweise Metallalkye, Metallhydride, Metallalkylhalogenide, Metallalkyloxide oder Metallalkyloxane, wobei die Metalle Elemente der Gruppen la, lla und/oder IIIa sind. Die Aktivatoren können beispielsweise mit weiteren Ester-, Ether-, Amin- oder Silylether-Gruppen modifiziert sein. Diese Katalysatorsysteme werden gewöhnlich als Philipps, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metallocen oder Single Site Katalysatoren (SSC) bezeichnet.

1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene as well as polymers of cycloolefins such as cyclopentene or norbornene; polyethylene (which may or may not be crosslinked); e.g. high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLPE), branched low density polyethylene (VLDPE). Polyolefins, ie polymers of monoolefins, as mentioned by way of example in the previous paragraph, in particular polyethylene and polypropylene, can be produced by various processes, in particular by the following methods:

a) radical (usually at high pressure and temperature)

b) by means of a catalyst, the catalyst usually containing one or more metals from Group IVb, Vb, VIb or VIII. These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either π- or σ-coordinated. These metal complexes can be free or fixed on supports, such as on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts as such can be active in the polymerization, or further activators can be used, such as, for example, metal alkyds, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements from groups Ia, IIIa and / or IIIa. The activators can be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Philipps, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for. B. Mixtures of polypropylene with polyisobutylene, polyethylene with polyisobutylene, polypropylene with polyethylene (e.g. PP / HDPE / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE) among themselves.

3. Copolymers of mono- and diolefins with one another or with others Vinyl monomers such as e.g. Ethylene-propylene copolymers, linear polyethylene lower Density (LLDPE) and blends thereof with low density polyethylene (LDPE), Propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, Ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, Ethylene-octene copolymers, propylene-butadiene copolymers, Isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and a diene, such as Hexadiene, dicyclopentadiene or ethylidenorbornene; also mixtures of such Copolymers with one another and with polymers mentioned under 1), e.g. Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or random Polyalkylene / carbon monoxide copolymers and their blends with others Polymers such as Polyamides.

4. Hydrocarbon resins (eg C ₅ -C ₉ ) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly (p-methylstyrene), poly- (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as e.g. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile methacrylate; Blends of high impact strength made from styrene copolymers and another Polymer, e.g. a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene, e.g. Styrene-butadiene-styrene, Styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

7. Graft copolymers of styrene or α-methylstyrene, e.g. Styrene on polybutadiene, Styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and Acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and Methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene; Styrene and alkyl acrylates or Alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, Styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, Styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their mixtures with the copolymers mentioned under 6), e.g. as so-called ABS, MBS, ASA or AES polymers are known.

8. Halogen-containing polymers such as e.g. Polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, Epichlorohydrin homo- and copolymers, especially polymers made from halogen-containing Vinyl compounds such as Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, Polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, Vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

9. Polymers derived from α, ss-unsaturated acids and their derivatives, such as Polyacrylates and polymethacrylates, impact modified with butyl acrylates Polymethyl methacrylates, polyacrylamides and polyacrylonitriles.

10. Copolymers of the monomers mentioned under 9) with one another or with others unsaturated monomers, e.g. Acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, Acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or derive acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, -maleate, polyvinyl butyral, polyallylphthalate, polyallylmelamine; and their copolymers with olefins mentioned in point 1.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, Polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers.

13. Polyacetals, such as polyoxymethylene, and also such polyoxymethylenes, the comonomers, such as. Ethylene oxide included; Polyacetals made with thermoplastic polyurethanes, Acrylates or MBS are modified.

14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or Polyamides.

15. Polyurethanes, which are made up of polyethers, polyesters and polybutadienes terminal hydroxyl groups on the one hand and aliphatic or aromatic Derive polyisocyanates on the other hand, as well as their precursors.

16. Polyamides and copolyamides, which are derived from diamines and dicarboxylic acids and / or Derived aminocarboxylic acids or the corresponding lactams, such as polyamide 4, Polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides based on m-xylene, diamine and adipic acid; Polyamides, made from hexamethylenediamine and iso- and / or terephthalic acid and optionally an elastomer as a modifier, e.g. Poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene-isopthalamide. Block copolymers the aforementioned polyamides with polyolefins, olefin copolymers, ionomeric, or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or Polytetramethylene glycol. Polyamides modified with EPDM or ABS or Copolyamides; and polyamides condensed during processing (“RIM polyamide systems”).

17. polyureas, polyimides, polyamideimides, polyetherimides, polyesteramides, Polyhydantoins and polybenzimidazoles.

18. Polyester, which is derived from dicarboxylic acids and dialcohols and / or Derive hydroxycarboxylic acids or the corresponding lactones, such as Polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, Polyhydroxybenzoates, as well as block polyether esters, which differ from Derive polyethers with hydroxyl end groups; also with polycarbonates or MBS modified polyester.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers that differ from aldehydes on the one hand and phenols, urea or Derive melamine, on the other hand, such as phenol-formaldehyde, urea-formaldehyde and Melamine formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins that differ from saturated and unsaturated copolyesters Dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds Derive crosslinking agents, as well as their halogen-containing, flame-retardant Modifications.

24. Crosslinkable acrylic resins derived from substituted acrylic acid esters, e.g. of epoxy acrylates, urethane acrylates or polyester acrylates.

25. alkyd resins, polyester resins and acrylic resins mixed with melamine resins, urea resins, Isocyanates, isocyanurates, polyisocyanates or epoxy resins are crosslinked.

26. Crosslinked epoxy resins, which differ from aliphatic, cycloaliphatic, derive heterocyclic or aromatic glycidyl compounds, e.g. products from Bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, using conventional hardeners such as. Anhydrides or amines can be crosslinked with or without accelerators.

27. Natural polymers such as cellulose, natural rubber, gelatin, and their polymer homologous chemically modified derivatives, such as cellulose acetates and propionates and butyrates, or the cellulose ethers, such as methyl cellulose; as well as rosins and derivatives.

28. Mixtures (polyblends) of the aforementioned polymers, such as e.g. PP / EPDM, Polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBT / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

29. Natural and synthetic organic substances, the pure monomeric compounds or mixtures of such, for example mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates), as well as Mixtures of synthetic esters with mineral oils in any Weight ratios, e.g. find use as spin finishes, as well their aqueous emulsions.

30. Aqueous emulsions of natural or synthetic rubbers, e.g. Natural rubber latex or latices of carboxylated styrene-butadiene copolymers.

According to the invention by the compounds of formula (1) or by a suitable one Combination with these compounds can stabilize organic material if necessary contain further additives, for example antioxidants, light stabilizers, Metal deactivators, antistatic agents, flame retardants, lubricants, Nucleating agents, acid scavengers (basic costabilizers), pigments and fillers. Antioxidants and light stabilizers, in addition to the compounds (1) or combinations are added, for example, compounds based on sterically hindered Containing amines or sterically hindered phenols or sulfur or phosphorus Costabilizers. Suitable additives that can also be used in combination are For example, connections can be used as listed below:

1. Antioxidants

1.1 Alkylated monophenols, e.g. 2,6 di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a-methyl-cyclohexyl) -4,6-dimethyl-phenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or in the side chain branched nonylphenols, such as. B. 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6 (1'-methyl-undec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) phenol and mixtures thereof.

1.2 alkylthiomethylphenols, e.g. 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3 hydroquinones and alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxy-phenyl) adipate.

1.4 Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- (6-tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec.-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.5 alkylidene bisphenols, e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis- [4-methyl-6- (α-methylcyclo-hexyl) phenol], 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methyl- phenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, Bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, Bis- [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'- hydroxyphenyl) butyrate].

1.6 O-, N- and S-benzyl compounds, e.g. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, Octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) amine, Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydro-xybenzyl-mercaptoacetate, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate.

1.7 Hydroxybenzylated malonates, e.g. Dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, Di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, Di- [4 (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.8 hydroxybenzyl aromatics, e.g. B. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.9 triazine compounds, e.g. 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert -butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl -4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1. 10 benzylphosphonates, e.g. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

1.11 acylaminophenols, e.g. 4-hydroxy lauric anilide, 4-hydroxy stearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.

1.12 esters of ss- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyvalent Alcohols, such as with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

1.13 esters of ss- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with one or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, Octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Neopentyl glycol, thiodiety glycol, diethylene glycol, triethylene glycol, pentaerythritol, Tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

1.14 esters of ss- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyvalent Alcohols, e.g. Methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo (2,2,2) octane.

1.15 esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent Alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

1.16 esters of 3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyric acid with mono- or polyvalent Alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

1.17 amides of ss- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, e.g. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine.

1.18. Chroman derivatives such as Tocopherol (α-tocopherol, ss-tocopherol, γ-tocopherol, δ-tocopherol) as well as mixtures thereof (vitamin E) and other mixtures among themselves .

1.19. Ascorbic acid (vitamin C).

1.20. Amine antioxidants, such as. B. N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di (naphthyl-2 -) - p-phenylenediamine, N-isopropyl, N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenyl-amine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. B. p, p'-di-tert-octyl-diphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-di-aminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'diaminodiphenylmethane, 1,2-di - [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di- [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, Mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, Mixture of mono- and dialkylated nonyldiphenylamines, Mixture of mono- and dialkylated do-decyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyl-di-phenylamines, mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-di-hydro-3,3-dimethyl-4H-1,4-benzothiazine, Phenothiazine, mixture of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, Mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N'-tetra-phenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene diamine, Bis- (2,2,6,6-tetra-methylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorber and light stabilizer

2.1 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -benztriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) -benztriazole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] -benztriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5- chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ' , 5'-Di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, mixture of 2- ( 3'-tert-Butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-Butyl-5' - [2- (2-ethylhexyloxy ) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2 - (3'-tert-Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-oc tyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'- hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2,2'-methylene-bis- [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; Transesterification product of 2- [3'-tert-butyl-5 '(2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO (CH ₂ ) ₃ ] - ₂ with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.

2.2 2-hydroxybenzophenones, e.g. 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivative.

2.3 esters of optionally substituted benzoic acids, e.g. 4-tert-butylphenyl salicylate, Phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) resorcinol, Benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butylphenyl ester.

2.4 Acrylates such as α-cyan-ss, ss-diphenylacrylate or isooctyl ester, α-carbomethoxycinnamic acid methyl ester, α-Cyano-ss-methyl-p-methoxycinnamic acid methyl ester or butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (ss-carbo-methoxy-ss-cyanovinyl) -2-methylindoline.

2.5 nickel compounds such as Nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3 tetramethylbutyl) phenol] such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, Nickel dibutyl dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butyl-benzylphosphonic acid monoalkyl esters, like the methyl or ethyl ester, Nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecylketoxim, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

2.6 Sterically hindered amines, such as, for example, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) glutarate, bis - (2,2,6,6-tetramethyl-piperidin-4-yl) succinate, bis- (1,2,2,6,6-pentamethyl-piperidin-4-yl) sebacate, bis- (1,2, 2,6,6-pentamethylpiperidin-4-yl) glutarate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester , 2,2,6,6-tetramethylpiperidyl behenate, 1,2,2,6,6-pentamethyl piperidyl behenate, condensation product from 1-hydroxyethyl-2,2,6,6-tetra-methyl-4-hydroxypiperidine and succinic acid, condensation product from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-s-triazine, Tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraoate, 1,1 1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6 -tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetrame thylpiperidine, 4-stearyloxy-1,2,2,6,6-pentamethylpiperidine, 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine, bis- (1,2,2,6,6-pentamethylpiperidyl) - 2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (4-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2, 4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, condensation product from N, N ' Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of N, N'-bis (2, 2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product from 2-chloro-4,6-di- (4-n- butylamino-2,2,6,6-tetramethyl-piperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di- (4th -methoxypropylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di- (4-methoxypropylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis - (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1, 2-bis- (3-aminopropylamino) ethane, reaction products of 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine - or polyvalent amines, replacing between one and all active H atoms on the amine, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, reaction products of 2-chloro-4, 6-di- (4-n-butylamino-1,2,2,6,6-penta-methylpiperidyl) -1,3,5-triazine with mono- or polyvalent amines, where between one and all active H atoms on Amine are replaced, such as with ethylenediamine, di-ethylenediamine, triethylenetetramine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, reaction products of 2-chloro-4,6-di - (4-n-Butylamino-2,2,6,6-tetra-methyl-piperidyl) -1,3,5-triazine and 4-tert-octylamino-2,6-dichloro-1,3,5-s -triazine with mono- or polyvalent amines, where between one and all active H atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, reaction products of 2- Chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 4-tert-octylamino-2,6-dichloro-1, 3,5-s-triazine with mono- or polyvalent amines, replacing between one and all active H atoms on the amine, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1,2-bis (3-amino -propylamino) ethane, reaction products of 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 4- (4-n- Butylamino-2,2,6,6-tetramethyl-piperidyl) -2,6-dichloro-1,3,5-s-triazine with mono- or polyvalent amines, wherein between one and all active H atoms on the amine are replaced , how with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, reaction products of 2-chloro-4,6-di- (4-n-butylamino-1,2,2), 6,6-pentamethyl-piperidyl) -1,3,5-triazine and 4- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -2,6-dichloro-1,3,5-s triazine with mono- or polyvalent amines, where between one and all active H atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, condensation product 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine, N- (2,2, 6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 8-acetyl-3-dodecyl-7,7 , 9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, oligomerized 2,2,4,4-tetramethyl-20- (oxiranylmethyl) -7-oxa-3, 20-diaza-dispiro [5.1.11.2] heneicosan-21-one, oligomerized 1,2,2,4,4-pentamethyl -20- (oxiranylmethyl) -7-oxa-3,20-diazadispiro [5.1.11.2] heneicosan-21-one, oligomerized 1-acetyl-2,2,4,4-tetramethyl-20- (oxiranylmethyl) -7 -oxa-3,20-diaza-dispiro [5.1.11.2] heneicosan-21-one, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20- diazadispiro [5.1.11.2] heneicosan-21-one, 2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diazadispiro [5.1.11.2] hen-eicosan-3- propanoic acid dodecyl ester, 2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diaza-dispiro [5.1.11.2] heneicosane-3-propanoic acid tetradecyl ester, 2,2,3,4, 4-pentamethyl-7-oxa-3,20-diazadispiro [5.1.11.2] heneicosan-21-one, 2,2,3,4,4-penta-methyl-7-oxa-21-oxo-3,20 -diaza-dispiro- [5.1.11.2] heneicosan-3-propanoic acid dodecyl ester, 2,2,3,4,4-pentamethyl-7-oxa-21-oxo-3,20-diazadispiro- [5.1.11.2] -heneicosan 3-propanoic acid tetradecyl ester, 3-acetyl-2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [5.1.11.2] heneico-san-21-one, 3-acetyl-2,2 , 4,4-tetrameth yl-7-oxa-21-oxo-3.20-diaza-dispiro [5.1.11.2] hen-eicosan-3-propanoic acid dodecyl ester, 3-acetyl-2,2,4,4-tetramethyl-7-oxa -21-oxo-3,20-diazadispiro [5.1.11.2] heneicosane-3-propanoic acid tetradecyl ester, 1.1 ', 3.3', 5.5'-hexa-hydro-2.2 ', 4.4' , 6,6'-hexaaza-2,2 ', 6,6'-bismethano-7,8-dioxo-4,4'-bis- (1,2,2,6,6-penta-methyl-4- piperidyl) biphenyl, poly-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,8-diaza-decycles, addition compound of 2,2,6,6-tetramethyl- 4-allyloxypiperidine and poly-methylhydrogensiloxane (molecular weight up to 4000), addition compound of 1,2,2,6,6-pentamethyl-4-allyloxypiperidine and polymethylhydrogensiloxane (molecular weight up to 4000), N, N'-diformyl-N , N'-bis- (2,2,6,6-tetramethyl-4-piperidinyl) hexamethylenediamine, N, N'-di-formyl-N, N'-bis- (1,2,2,6,6 -pentamethyl-4-piperidinyl) -hexamethylenediamine, 5,11-bis- (2,2,6,6-tetramethyl-4-piperidinyl) -3,5,7,9,11,13-hexaaza-tetracyclo- [7.4 .0.0 ^2.7 .1 ^3.13 ] -tetradecane-8,14-dione, 5,11-bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) -3,5,7, 9,11,13-hexaazatetracyclo- [7.4.0.0 ^2.7 .1 ^3.13 ] tetradecane-8,14-dione, [(4-methoxyphenyl) methylene] propanedioic acid bis- (2,2,6,6-tetramethyl-4-piperidinyl ) ester, [(4-methoxyphenyl) methyl-en] propanedioic acid bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,4,6-tris (N -cyclohexyl-N- [2- (3,3,4,5,5-pentamethyl-piperazinon-1-yl) -ethyl] -amino) -1,3,5-triazine, copolymer of styrene reacted with methylstyrene and maleic anhydride with 4-amino-2,2,6,6-tetramethylpiperidine and octadecylamine, copolymer of styrene with α-methylstyrene and maleic anhydride reacted with 4-amino-1,2,2,6,6-pentamethylpiperidine and octadecylamine, polycarbonate with 2, 2 '- [(2,2,6,6-tetramethyl-4-piperidinyl) imino] bis [ethanol] as diol component, polycarbonate from 2,2' - (1,2,2,6,6-pentamethyl -4-piperidinyl) -imino] -bis- [ethanol] as a diol component, copolymer of maleic anhydride and an α-olefin to C30 reacted with 4-amino-2,2,6,6-tetramethylpiperidine, copolymer of maleic anhydride and an α- Olefin implemented to C ₃₀ m it 1-acetyl-4-amino-2,2,6,6-tetramethylpiperidine, copolymer of maleic anhydride and an α-olefin to C ₃₀ reacted with 4-amino-1,2,2,6,6-pentamethylpiperidine, and the N-alkyl and N-aryloxy derivatives of the above-mentioned compounds with free NH groups on the piperidine, especially α-methylbenzyloxy and alkyloxy from C ₁ to C ₁₈ .

2.7 oxalic acid diamides, e.g. 4,4'-di-octyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy and of o- and p-ethoxy-di-substituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazines, e.g. 2,4,6-tris- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4 ', 6-bis- (2', 4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl-phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyloxy / tridecyloxy-2-hydroxyprop-oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.

3. Metal deactivators, e.g. N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, Oxanilide, isophthalic acid dihydrazide, sebacic acid bisphenyl hydrazide, N, N'-diacetyladipic acid dihydrazide, N, N'-bis-salicyloyloxalic acid dihydrazide, N, N'-bis-salicyloylthiopropionic acid dihydrazide.

4. Phosphites and phosphonites such as e.g. Triphenyl phosphite, diphenylalkyl phosphites, Phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, Diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6, -di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, Bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerytritol diphosphite, Tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphophocin, Bis- (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tris (2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butyl) - phenyl-5-methyl) phenyl phosphite, 2,2 ', 2 "nitrilo [triethyl-tris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], Bis [2-methyl-4,6-bis (1,1-dimethylethyl) phenol] ethyl phosphate.

5. Hydroxylamines, such as. B. N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamines made from hydrogenated tallow fatty amine.

6. Nitrons, such as B. N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octylalphaheptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecylalpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alphaheptadecylnitrone, N-octa-decyl-alpha-hexadecylnitrone, nitrones derived from N, N-dialkylhydroxylamines, made from hydrogenated tallow fatty amines.

7. Zeolites and hydrotalcites, such as. B. DHT 4A. Such hydrotalcites can according to the general formula [(M ²⁺ ) _1-x (M ³⁺ ) _x (OH) ₂ (A ^n- ) _{x / n} yH ₂ O], are described, whereby

(M ²⁺ )

Mg, Ca, Sr, Ba, Zn, Pb, Sn, Ni

(M ³⁺ )

Al, B, Bi

On

an anion of valence n

n

an integer from 1-4

x

a value between 0 and 0.5

y

a value between 0 and 2; means.

A

means OH ^- , Cl ^- , Br ^- , l ^- , ClO ₄ -, CH ₃ COO ^- , C ₆ H ₅ COO ^- , CO ₃ ^2- , SO ₄ ^2- , (OOC-COO) ² , (CHOHCOO) ₂ ^2- , HO (CHOH) ₄ CH ₂ COO ^- , C ₂ H ₄ (COO) ₂ ^2- , (CH ₂ COO) ₂ ^2- , CH ₃ CHOHCOO ^- , SiO ₃ ^2- , SiO ₄ ^4- , Fe ( CN) ₆ ^3- , Fe (CN) ₆ ^4- , BO ₃ ^3- , PO ₃ ^3- , HPO ₄ ^2- ,

Hydrotalcites are preferably used, in which (M ²⁺ ) for (Ca ²⁺ ), (Mg ²⁺ ) or a mixture of (Mg ²⁺ ) and (Zn ²⁺ ); (A ^n- ) stand for CO ₃ ^2- , BO ₃ ^3- , PO ₃ ^3- . x has a value of 0 to 0.5 and y has a value of 0 to 2. Furthermore, hydrotalcites that have the formula [(M ²⁺ ) _x (Al ³⁺ ) ₂ (OH) _{2x + 6nz} (A ^n- ) ₂ yH ₂ O] can be used. Here (M ²⁺ ) stands for Mg ²⁺ , Zn ²⁺ , but preferably Mg ²⁺ . (A ^n- ) stands for an anion, especially from the group CO ₃ ^2- , (OOC-COO) ^2- , OH ^- and S ^2- , where n describes the valence of the ion.

y

stands for a positive number, preferably between 0 and 5, very particularly between 0.5 and 5. x and z have positive values which are preferably between 2 and 6 at x and should be less than 2 at z. The hydrotalcites of the following formulas are particularly preferred:

Al 2 O 3rd x 6MgO x CO 2 x 12H 2 O, Mg 4.5 Al 2 (OH) 13 x CO 3rd x 3.5H 2 O, 4MgO x Al 2 O 3rd x CO 2 x 9H 2 O, 4MgO x Al 2 O 3rd x CO 2 x 6H 2 O, ZnO x 3MgO x Al 2 O 3rd x CO 2 x 8-9H 2 O, ZnO x 3MgO x Al 2 O 3rd x CO 2 x 5-6H 2 O, Mg 4.5 Al 2 (OH) 13 x CO 3rd , Hydrotalcites are preferably used in the polymer in a concentration of 0.01 to 5% by weight, particularly 0.2 to 3% by weight, based on the total polymer preparation.

8. Thiosynergists, such as B. Thiodipropionsäuredilaurylester or Thiodipropionsäuredistearylester.

9. Peroxide destroying compounds such as Esters of ss-thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, Mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc alkyldithiocarbamate, Zinc dibutyl dithio carbamate, dioctadecyl monosulfide, Dioctadecyl disulfide, pentaerythritol tetrakis (ss-do-decylmercapto) propionate.

10. Polyamide stabilizers such as e.g. Copper salts in combination with iodides and / or Phosphorus compounds and salts of divalent manganese.

11. Basic co-stabilizers such as Melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, Urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, Alkali and alkaline earth salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate or Tin catecholate, alkali and alkaline earth salts as well as the zinc salt or the aluminum salt of lactic acid.

12. Nucleating agents, e.g. inorganic substances, such as B. talc, metal oxides such. B. Titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of preferably Alkaline earth metals, organic compounds such as mono- or polycarboxylic acids as well as their salts, such as. B. 4-tert-butylbenzoic acid, adipic acid; Diphenylacetic acid; Sodium succinate or sodium benzoate; Acetals of aromatic Aldehydes and polyfunctional alcohols such. B. sorbitol, e.g. 1,3-2,4-di (benzilidene) -D-sorbitol, 1,3-2,4-di (4-tolylidene) -D-sorbitol, 1,3-2,4-di (4-ethylbenzilidene) -D-sorbitol, polymeric compounds, such as. B. ionic copolymers ("ionomers").

13. Fillers and reinforcing agents such as e.g. Calcium carbonate, silicates, glass fibers, Asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, soot, Graphite, wood flour and other flours or fibers of other natural products, synthetic Fibers.

14.Other additives, such as Plasticizers, lubricants, emulsifiers, pigments, Rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, Antistatic agents, blowing agents.

The additives of the general formula (1) or the combinations described are according to the generally accepted methods in the organic material, preferably in the Polymers incorporated. The incorporation can, for example, by mixing in or Application of the compounds and optionally other additives in or on the Polymers immediately before, during or after the polymerization or in the Polymer melt take place before or during shaping. Also by applying the dissolved or dispersed compounds on the polymer directly or mixing into one Solution, suspension or emulsion of the polymer, if necessary with subsequent Evaporation of the solvent, the incorporation can take place. The connections are too effective if they are subsequently in a granulated polymer in a separate Processing step are introduced. The compounds of formula (1) can also in Form of a masterbatch containing these compounds, for example, in a concentration contains from 1 to 75, preferably 2.5 to 30 wt .-%, the polymers to be stabilized be added.

EXPERIMENTAL PART

The following examples are intended to explain the invention in greater detail, without this in any Way to narrow it down.

EXAMPLES 1-6 Production of the new compounds according to the invention

In a closed reaction vessel, 0.35 mol of 2,2,5,5-tetramethylpiperidin-4-one is stirred into 80 g of glacial acetic acid while cooling with ice. The mixture is heated to 60 ° C. in the closed apparatus. 0.40 mol of hydrocyanic acid are then added. The reaction mixture is stirred at 50 ° C for 3 h. After cooling to about 20 ° C., 0.70 mol of ketone (or aldehyde) and 40 g of glacial acetic acid are added. Hydrogen chloride is passed into the solution while cooling with ice until the reaction mixture has taken up 0.80 mol of hydrogen chloride. The mixture is stirred at 80 ° C. for 5 h and then freed from the volatile constituents in vacuo. After adding 200 ml of acetone, the hydrochloride of the respective target compound is filtered off, washed twice with 50 ml of acetone each time and dried in vacuo at 80.degree. This hydrochloride is stirred with 1000 ml of water and adjusted to pH 9 using 30% sodium hydroxide solution. The resulting precipitate is filtered, washed twice with 50 ml of water each time and dried in vacuo at 80 ° C. The desired product is isolated in the form of a white to beige, finely crystalline powder. Summary of the properties of the new compounds according to the invention (with reference to formula (1): X ₁ = H; X ₂ = H) No. X ₃ X ₄ Melting point yield 1 -CH _3rd -CH (CH ₃ ) - (CH ₂ ) -CH ₃ 140-144 ° C 77% 2 -CH _3rd - (CH ₂ ) -C (CH ₃ ) ₃ 192-194 ° C 58% 3rd -CH _3rd - (CH ₂ ) ₂ -CH (CH ₃ ) ₂ 152-153 ° C 85% 4th - (CH ₂ ) -CH ₃ - (CH ₂ ) -CH (CH ₃ ) - (CH ₂ ) -CH ₃ 114-116 ° C 68% 5 H - (CH ₂ ) -CH (CH ₃ ) ₂ 189-190 ° C 72% 6 H -CH (CH ₃ ) ₂ 150-151 ° C 65%

EXAMPLES 7-11 Preparation of the comparative compounds not according to the invention

Comparative compounds 7-11 are prepared according to the general method described above. Summary of the properties of the comparative compounds not according to the invention (with reference to formula (1): X ₁ = H; X ₂ = H) No. X ₃ X ₄ Melting point yield 7 Together with X ₄ : - (CH ₂ ) ₁₁ - 221-222 ° C 88% 8th H - (C ₆ H ₅ ) 264-265 ° C 83% 9 H -para- (C ₆ H ₄ ) -C (CH ₃ ) ₃ 254-264 ° C 80% 10 H -para- (C ₆ H ₄ ) -O- (CH ₃ ) 223-225 ° C 75% 11 - (CH ₂ ) -CH ₃ - (C ₆ H ₅ ) 192-194 ° C 67%

EXAMPLE 12

Melt stabilization of polypropylene, which is stabilized with the sterically hindered amines under consideration to slow down the thermal degradation during polymer processing. 100 parts of polypropylene powder, type Eltex P HL 001PF (manufacturer Solvay Polyolefines) together with the basic stabilization consisting of 0.05 part of pentaerythrityl tetrakis-3- (3,5-di-tert.butyl-4-hydroxyphenyl) propionate (Irganox 1010 ; Manufacturer Ciba Specialty Chemicals) and 0.10 parts Ca stearate, 0.05 parts tris (2,4-di-tert.butylphenyl) phosphite (Irgafos 168; manufacturer Ciba Specialty Chemicals) and 0.15 parts of the sterically hindered piperidine derivative (e.g. Formula Type 1) mixed in a laboratory mixer, type Major (manufacturer Kenwood). A pre-extrusion was carried out in a single-screw laboratory extruder (screw diameter 25 mm; UD = 25; compression 1: 3) (manufacturer Collin) at 80 rpm with the mixture thus produced. performed at T = 220 ° C. The multiple extrusion (1st-5th passage) of the mixture was carried out in the same extruder with a screw rotation speed of 50 rpm. at a temperature of all extruder zones of T = 230 ° C through a nozzle with a diameter of 4 millimeters. The melt index was determined at T = 230 ° C. using a melt index measuring device type 4105 from the manufacturer Zwick using a standard weight of 2.16 kg. The color (Yl) of the granules was determined using a spectrocolorimeter, type CM 3500d (manufacturer Minolta). Table 3 shows the results of multiple extrusion under the conditions described. Multiple extrusion of polypropylene (3rd generation) at T = 230 ° C; the polymer contains the following components as basic additives: 0.05% pentaerythrityl tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1010; manufacturer Ciba Specialty Chemicals); 0.05% tris (2,4-di-tert.butylphenyl) phosphite (Irgafos 168; manufacturer Ciba Specialty Chemicals) and 0.10% calcium stearate; the concentration of the sterically hindered piperidine derivative (HAS) is 0.15% in each case. Verse.- HAS Melt Flow index (MFI) colour (YI) No. Pre-extr. 1.Extr. 3.Extr. 5.Extr. Pre-extr 1.Extr. 3.Extr. 5.Extr 1 without HAS 2.62 3.04 3.74 3.84 3.28 11.23 13.54 15.13 2 Tin. 770 2.74 2.92 3.27 3.94 4.77 11.81 14.84 17.29 3rd Host. N 20 2.74 2.89 3.28 3.64 2.52 8.41 May 11 13.14 4th Connection 4 2.96 2.97 3.01 3.21 4.09 9.33 7.79 6.8

EXAMPLE 13

Artificial weathering of polypropylene, which is stabilized with the sterically hindered amines considered to slow down UV degradation. After the first extrusion of the test described in Example 12, samples were first used for 90 seconds at a pressure of 50 kN using a Fontjne type heating press at a temperature of T = 230 ° C., and then after being relaxed for 90 seconds at a pressure of 500 kN processed into films (thickness approx. 100 µm). The exposure was carried out with the aid of a UV-CON A device (max. Wavelength λ = 340nm) with exposure cycles of 24 hours at a temperature of the black boards of T = 50 ° C. The decomposition of the sample was monitored by means of the carbonyl absorption monitored by means of IR spectroscopy (device type FTS 155, manufacturer Bio-Rad). The time (in hours) during which an increase in carbonyl absorption of 0.3 units was observed was determined. The results are shown in Tab. 4. Artificial weathering time, until ΔCO> 0.3 units. Liaison 4th 7 8th 9 10 11 time 1760 h 1532 h 1218 h 1034 h 615 h 1465 h

It is clearly visible that the connection 4 according to the invention differs significantly from that comparative compounds according to the invention.

Claims (10)

Stabilizers of the general formula (1)

wherein

X ₁

Hydrogen, a C ₁ -C ₂₂ alkyl group; an oxygen radical O *; -OH; -NO; -CH ₂ CN; Benzyl; Allyl; a C ₁ -C ₃₀ alkoxy group; a C ₅ -C ₁₂ cycloalkyloxy group; a C ₆ -C ₁₀ aryloxy group, where the aryl radical can additionally be substituted by a C ₁ -C ₅ alkyl group or a halogen or a nitro group; a C ₇ -C ₂₀ arylalkyloxy group, where the aryl radical can additionally be substituted by a C ₁ -C ₅ alkyl group or a halogen or a nitro group; a C ₃ -C ₁₀ alkenyl group; a C ₃ -C ₆ alkynyl group; a C ₁ -C ₁₀ acyl group; Halogen; is an unsubstituted or substituted by C ₁ -C ₄ alkyl phenyl radical;

X ₂

Hydrogen, a [CH ₂ -CH ₂ -C (O) -OX ₅ ] residue, a [CH ₂ -C (CH ₃ ) HC (O) -OX ₅ ] residue; represents a C ₁ -C ₂₂ alkyl group;

X ₃ and X ₄

independently of one another hydrogen, an unsubstituted or substituted by C ₁ -C ₄ alkyl or a C ₁ -C ₂₂ alkyl group, at least one of the two radicals X ₃ or X _{4 being} a branched C ₄ -C ₂₂ alkyl group; and in what

X ₅

represents a C ₁ -C ₂₂ alkyl group.

Mixture of a compound of the general formula (1) according to Claim 1 with one or more stabilizers based on sterically hindered amines of the formulas A1 to A10,

wherein

R ¹

Hydrogen, C ₅ -C ₇ cycloalkyl or a C ₁ -C ₁₂ alkyl group and

R ⁴

either hydrogen or a C ₁ -C ₂₂ alkyl group, an oxygen radical O *, -OH, -NO-, CH ₂ CN, benzyl, allyl, a C ₁ -C ₃₀ alkoxy group, a C ₅ -C ₁₂ cycloalkyloxy group, a C ₆ -C ₁₀ aryloxy group, where the aryl radical may additionally be substituted, a C ₇ -C ₂₀ aralkyloxy group, where the aryl radical may additionally be substituted, a C ₃ -C ₁₀ alkenyl group, a C ₃ -C _6- alkynyl group, a C ₁ -C ₁₀ -acyl group, halogen, C ₇ -C ₉ -phenylalkyl which is unsubstituted or substituted on the phenyl ring by C ₁ -C ₄ -alkyl,

R ⁶

one or more times by hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, carboxy, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, or Acyl substituted aromatic radical,

O

1 or 2 means.

wherein

R ¹ and R ⁴

have the meanings given above,

p

1 or 2 and

for p = 1 R ⁷

C ₁ -C ₂₂ alkyl, C ₂ -C ₁₈ oxaalkyl, C ₂ -C ₁₈ thiaalkyl, C ₂ -C ₁₈ azaalkyl or C ₂ -C ₈ alkenyl,

for p = 2 R ⁷

C ₁ -C ₂₂ alkylene, C ₂ -C ₁₈ oxaalkylene, C ₂ -C ₁₈ thiaalkylene, C ₂ -C ₁₈ azaalkylene or C ₂ -C ₈ alkenylene.

wherein

R ¹ and R ⁴

have the meanings given above,

R ⁸ and R ⁹

independently of one another hydrogen, C ₁ -C ₆ alkyl, C ₇ -C ₁₂ aralkyl, aryl or carboxylic acid esters,

R ⁸ and R ⁹

together represent a tetra or pentamethyl group.

wherein

R ¹ and R ⁴

have the meanings given above,

R ² and R ³

independently of one another a hydrogen atom, a C ₁ -C ₁₈ alkyl group or together with the carbon atom connecting them a ring of ring size 5 to 13 or together with the carbon atom binding them a group of the formula (IV),

R ⁴ and R ⁵

independently of one another either hydrogen or a C ₁ -C ₂₂ alkyl group, an oxygen radical O *, -OH, -NO, -CH ₂ CN, benzyl, allyl, a C ₁ -C ₃₀ alkyloxy group, a C ₅ -C ₁₂ - Cycloalkyloxy group, a C ₆ -C ₁₀ aryloxy group, where the aryl radical may additionally be substituted, a C ₇ -C ₂₀ arylalkyloxy group, where the aryl radical may additionally be substituted, a C ₃ -C ₁₀ alkenyl group, a C ₃ -C ₆ -alkynyl group, a C ₁ -C ₁₀ -acyl group, halogen, C ₇ -C ₉ -phenylalkyl which is unsubstituted or substituted on the phenyl ring by C ₁ -C ₄ -alkyl,

q

a number of 1 or 2,

R ¹⁰

Hydrogen, methyl, phenyl or carb-C ₁ -C ₂₁ alkoxy,

R ¹¹

Hydrogen or methyl,

R ¹²

for q = 1 hydrogen, C ₁ -C ₂₁ alkyl, C ₂ -C ₂₂ alkenyl, C ₅ -C ₁₂ cycloalkyl, a radical of the formula

means, wherein R ¹ and R ^{5 have} the meaning given above, and

R ¹²

for q = 2 is C ₁ -C ₁₈ alkylene, C ₅ -C ₉ cycloalkylene or arylene.

where R ¹ , R ⁴ , R ⁷ and p have the above definitions.

where R ¹ , R ⁴ , R ⁷ and p have the above definitions.

in which

R ¹ , R ⁴

have the above definitions,

R ³⁰

Hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl or C ₇ -C ₉ phenylalkyl, and

a

means a number from 1 to 10.

in which

R ¹ and R ⁴

has the above meaning and

R ⁷

has the meaning defined in formula A2 for p = 1.

A product A10 obtainable by reacting a polyamine of the formula A10a with formula A10b:

in which

R ¹ , R ⁴ and R ³⁰

have the meaning given above,

n _{5 '} , n _{5 "} and n _5"'

is independently a number from 2 to 12.

Mixture of a compound of the general formula (1) according to Claim 1 with one or more polymeric HALS compounds of the formulas B1 to B7

wherein

R ¹

Hydrogen, C ₅ -C ₇ cycloalkyl or a C ₁ -C ₁₂ alkyl group,

R ¹³

Hydrogen or methyl,

R ¹⁴

a direct bond or C ₁ -C ₁₀ alkylene and

r

means a number from 2 to 50.

in which

R ¹ and R ⁴

have the meanings given above,

R ¹⁵ and R ¹⁸

independently of one another a direct bond or a group -N (R ²² ) -CO- R ²³ -CO-N (R ²⁴ ) -,

R ²² and R ²⁴

independently of one another hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₉ phenylalkyl, or a group of the formula

R ²³

a direct bond or C ₁ -C ₄ alkylene,

R ¹⁶ , R ¹⁷ , R ²⁰ , R ²¹

independently of one another hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, or a group of the formula B2a,

R ¹⁹

Is hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₇ -C ₉ phenylalkyl, phenyl or a group of the formula B2a and

s

is a number from 1 to 50.

in which

R ¹ , R ⁴ and s

have the meanings given above,

R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹

are independently a direct bond or C ₁ -C ₁₀ alkylene.

A product B4 obtainable by reacting a product obtained by reacting a polyamine of the formula B4a with cyanuric acid chloride with a compound of the formula B4b,

in which

R ¹ and R ⁴

have the meanings given above,

n _{5 '} , n _{5 "} and n _5"'

are independently a number from 2 to 12,

R ³⁰

has the meaning given above; where B4 is a compound of the formula B4-1, B4-2, B4-3

or a mixture thereof, wherein

n ₅

1 to 20,

R ⁴ and R ³⁰

have the meaning given above;

in which

r

has the meaning given for formula B1,

R ³¹ , R ³³ and R ³⁴

are independently hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ cycloalkyl, phenyl, substituted by -OH and / or C ₁ -C ₁₀ alkyl-substituted phenyl, C ₇ -C ₉ phenylalkyl substituted on the phenyl radical by -OH and / or C ₁ -C ₁₀ alkyl C ₇ -C ₉ -Phenylkalkyl or a group of the formula B5a,

wherein R ¹ and R ^{5 have} the meanings given above, and

R ³²

C ₂ -C ₁₈ alkylene, C ₅ -C ₇ cycloalkylene or C ₁ -C ₄ alkylene di (C ₅ -C ₇ cycloalkylene), or

the radicals R ³¹ , R ³² and R ³³

together with the nitrogen atoms to which they are attached form a 5- to 10-membered heterocyclic ring, and at least one of the radicals R ³¹ , R ³³ and R ^{34 represents} a group of the formula B5a.

wherein

R ³¹ , R ³² , R ³³ and r

have the meanings given above,

R ³⁵ and R ³⁶

can independently have the definition of R ³⁴ , or

R ³⁵ and R ³⁶

together with the nitrogen atom to which they are attached form a 5- to 10-membered heterocyclic ring, which in addition to the nitrogen heteroatom may contain one or more heteroatoms, preferably an oxygen atom, and at least one of the radicals R ³¹ , R ³³ , R ³⁵ and / or R ^{36 represents} a group of the formula (B5a).

in which

R ¹ and R ⁴

have the meaning given above,

s

has the meaning given in formula B3,

R ³⁷

C ₁ -C ₁₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ cycloalkyl, phenyl or C ₁ -C ₁₀ alkyl-substituted phenyl, and

R ³⁸

C ₃ -C ₁₀ alkylene.

Mixture of compounds of the general formula (1) according to Claim 1 and one or more phosphorus stabilizers of the general formulas C1 to C7

where the indices are integers and n 'for 2, 3 or 4; u for 1 or 2; t for 2 or 3; y for 1, 2 or 3; and z represents 1 to 6; A ', when n' is 2, alkylene of 2 to 18 carbon atoms; alkylene with 2 to 12 carbon atoms interrupted by -S-, -O- or -NR '₄; a remainder of one of the formulas

or is phenylene;

A '

when n '3 is a radical of the formula -C _r H _2r-1 ;

A '

when n 'is 4, the radical of the formula C is (CH2) 4-;

A "

has the meaning of A 'when n' is 2;

B '

a radical of the formula -CH ₂ -; -CHR ' ₄ -; -CR ' ₁ R' ₄ -; -S- or a direct bond; or C ₅ -C ₇ cycloalkylidene; or with 1 to 4 C ₁ -C ₄ alkyl radicals in position 3, 4 and / or 5 substituted cyclohexylidene,

D '

when u is 1, methyl and when u is 2, -CH ₂ OCH ₂ -;

E '

when y is 1, alkyl having 1 to 18 carbon atoms, phenyl, a radical of the formula -OR ' ₁ or halogen;

E '

when y is 2 is a radical of formula -OA "-O-;

E '

when y is 3, a radical of the formula R ' _{4 is} C (CH ₂ O) ₃ - or N (CH ₂ -CH ₂ -O-) ₃ ;

Q '

represents the remainder of an at least z-valent alcohol or phenol, which is bound to the P atom (s) via the alcoholic or phenolic O atom (s);

R ' ₁ , R' ₂ and R ' ₃

independently of one another alkyl having 1 to 30 carbon atoms; alkyl with 1 to 18 carbon atoms substituted with halogen, -COOR ₄ ', -CN or -CONR ₄ ' R ₄ '; alkyl interrupted by -S-, -O- or -NR ' ₄ - having 2 to 18 carbon atoms; Phenyl-C ₁ -C ₄ alkyl; Cycloalkyl of 5 to 12 carbon atoms; Phenyl or naphthyl; phenyl or naphthyl substituted with halogen, 1 to 3 alkyl radicals or alkoxy radicals with a total of 1 to 18 carbon atoms or with phenyl-C ₁ -C ₄ -alkyl; or a residue of the formula

where w is an integer ranging from 3 to 6;

R ' ₄

or the radicals R ' ₄ independently of one another are hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or phenylalkyl having 1 to 4 carbon atoms in the alkyl part;

R ' ₅ and R' ₆

are independently hydrogen, alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 or 6 carbon atoms;

R ' ₇ and R' ₈

in the case t = 2 independently of one another represent C ₁ -C ₄ -alkyl or together a 2,3-dehydropentamethylene radical; and

R ' ₇ and R' ₈

in the case t = 3, mean methyl;

the substituents R _'14

are independently hydrogen, alkyl of 1 to 9 carbon atoms or cyclohexyl;

the substituents R _'15

independently of one another hydrogen or methyl; and

R _'16

Represents hydrogen or C ₁ -C ₄ alkyl and, in the event that a plurality of radicals R _'16 are present, the radicals R' _{16 are} identical or different;

X 'and Y'

each represent a direct bond or -O-; and

e.g.

a direct bond; -CH ₂ -; -C (R _'16 ) ₂ - or -S-.

Mixture of compounds of general formula (1) according to claim 1 and UV absorbers from the class of the 2-hydroxybenzophenones, 2-hydroxyphenylbenztriazoles, Cinnamic acid derivatives or the oxanilides. Mixture according to claims 1 to 5, characterized in that the proportion of compounds of formula (1) is between 1 and 99% by weight. Mixture of compounds of general formula (1) according to claim 1 and Zeolites or hydrotalcites. Mixture of compounds of general formula (1) according to claim 1 alone or in mixtures according to claims 1 to 4 and one or more N, N-dialkyl-substituted Hydroxylamines. Mixture of compounds of general formula (1) according to claim 1 and one or more basic or other acid-binding costabilizers the group of metal carboxylates, oxides, hydroxides, carbonates and / or zeolites, and / or hydrotalcites. Use of stabilizers according to claims 1 or of mixtures according to claims 2 to 9 for stabilizing organic material.